Carbene precursor compound for producing an adhesive surface on a substrate

ABSTRACT

A process for producing a substrate having an adhesive surface, which process comprises: (a) contacting the substrate with a carbene precursor, which carbene precursor is a compound of the following formula (1): whose substituent groups are defined herein, provided that when R is aryl or heteroaryl, said aryl or heteroaryl may be substituted by one, two, three, four or five groups, which groups are independently selected from various groups including -L B -W B ; and (b) either: (i) when W A  or W B  comprises an adhesive functional group, generating a carbene reactive intermediate from the carbene precursor so that it reacts with the substrate to functionalise the surface, thereby yielding said substrate having an adhesive surface; or (ii) when W A  or W B  comprises a group which is a precursor of an adhesive functional group, generating a carbene reactive intermediate from the carbene precursor so that it reacts with the substrate to functionalise the surface, and (c) converting said group which is a precursor into an adhesive functional group thereby yielding said substrate having an adhesive surface. The invention further relates to carbene precursor compounds for use in the process, substrates produced by the process and to processes for preparing certain precursor compounds.

This application is the U.S. national phase of International ApplicationNo. PCT/GB2007/003194, filed 22 Aug. 2007, which designated the U.S. andclaims priority to Great Britain Application no. 0616724.1, filed 23Aug. 2006, the entire contents of which are hereby incorporated byreference.

FIELD OF INVENTION

The present invention relates to a process for producing a substratehaving an adhesive surface using an arylcarbene as the reactiveintermediate. The process allows the ability of a substrate to adhere toother materials to be tailored. Other surface properties, includingdispersability, hydrophobicity, hydrophilicity, oleophobicity andoleophilicity, may also be controlled by application of this inventionas desired. The invention in particular relates to a process forproducing a polymeric or an inorganic substrate which is capable ofadhesion to a further material. The invention further relates to carbeneprecursor compounds for use in the process, substrates produced by theprocess and to processes for preparing certain precursor compounds.

Modern technology and products are critically dependent on the use ofadvanced materials with properties carefully tailored to the desiredspecific application. These properties can rarely be achieved with onehomogeneous material, but are readily available by coating or laminatingone material onto another, giving a composite whose properties combinethe desired properties of each component. Of particular importance isthe achievement of nanolayer surface modifications, since this changesthe surface characteristics of the polymer, but without changing thebulk (e.g. mechanical strength) properties of the substrate. Suchcomposite materials possessing hybrid properties find wide applicationin the aeronautical, automotive, hygiene, computing, and consumerproduct industries, frequently as components which are critical forsuccessful function of a device or product. Such high value-addedplastic and polymeric materials can, however, be expensive to produce,since each polymer hybrid-needs to be individually designed and testedfor optimal properties, and downstream development and production costscan represent a significant barrier to their adoption.

Polymers are well known for their wide availability and low cost, andhave been used for a myriad of product applications. However, it is verycommon for their superior performance in one area to be compromised by apoor or less than desirable performance in another. The performance ofany polymeric material in a given application will depend upon any of anumber of characteristics, including brittleness, flexibility, colour,thermal and light stability, solvent resistance and biocompatibilityamongst many others. Although these properties might be desired orrequired, deficiencies often arise in polymer performance because thesemacroscopic properties are compromised by undesirable or unsuitablesurface characteristics. Alternatively, it would be of substantial valueif a method for the reliable modification of a polymer surface wereavailable so that novel surface characteristics could be introduced ontoa polymer. Thus, it would be highly advantageous to be able tomanipulate macroscopic properties and surface characteristicsindependently, so as to maintain favoured bulk properties of thepolymer, but to adjust surface properties to suit a given application,and this approach has received some attention; common methods includeabrasion and sand blasting, chemical treatment, and surface activation.Amongst the latter, a diversity of techniques has been developed: atombombardment, plasma treatment, ion implantation, laser treatment,electron beam, and welding are all well known. Although effective andwidely used in industrial applications, the disadvantage with many ofthese techniques is their high operating cost and large infrastructurerequirements, which makes them unsuitable for a wide spectrum ofapplications. Polymer surface modification has been reported usingchemical surface treatments; for example, cured epoxy polymerscontaining reactive hydroxyl groups were chemically modified withtrichlorotriazine followed by either iminodiacetic acid or imidazole, inorder to enhance the electrochemical deposition of copper.

Adhesion of polymeric materials is of particular importance in adiversity of applications, since this determines the nature of thesurface interaction of a polymer with its environment, and someimportant causative factors for adhesion have been reported such as thedensity of functional groups and surface topography. Adhesion can alsobe important in fibre-polymer composite materials and in co-extrusion.However, although understanding of the factors which determineinterfacial effects is increasingly advanced, using this knowledge todesign preferred surface characteristics is still in its infancy. Oneapproach for the modification of the adhesion-characteristics is tomodify the bulk polymer itself; for example, acrylates which arepolymerised in the presence of a vegetable extract from Asclepiassyriaca exhibit improved adhesive properties, although thepolymerisation step is slowed; cross-linking in acrylovinylic polymersfollowed by corona discharge or cold plasma treatment can improveadhesion. An important disadvantage of this approach is that, in orderto achieve surface modification, the entire bulk characteristics of thepolymer are changed, which is highly undesirable if the enhancement ofsurface properties comes at the expense of the required bulk properties.Surface grafting using physical treatments can alter a variety ofproperties, but as discussed above, can be limited by cost andinfrastructure requirements. Chemical pre-treatment of polyimidepolymers by sulfonation and by hydroxide can enhance metallisation(silver), but this is achieved by chemical degradation of the surface.

Diverse applications for surface modified polymers range from foodpackaging, to the incorporation of disinfecting function. Themodification of bacterial adhesion has been studied and, for example,polystyrene modified with polyethylene oxide and polypropylene oxideexhibits anti-adhesive effects with Staphylococcus epidermidis. Theincorporation of bactericidal activity and prevention of biofilmformation has been shown to be possible, and so has the reverse, theimprovement of biocompatibility. A further application of significanceis the metallisation of polymer surfaces of relevance in printed circuitboard and electronic technology.

In particular, a trend towards increased use of low surface energypolymers such as polyethylene and polypropylene is driven by a number offactors including the regulatory framework which requires thereplacement of polymers such as polystyrene, PVC and teflon for lesstoxic alternatives; favourable polymer feedstock prices; their ease ofmoulding and shaping; their suitability for packaging applications; andenvironmental and recycling considerations. However, it has been notedthat PPP and PE cannot normally be surface activated, because their lowsurface energy inhibits wetting by a solvent. Thus, the key advantage ofthese polymers in many applications—their inertness—can become their keylimitation, since this inertness prevents novel polymeric functions tobe developed.

There is therefore a continuing need to develop an improved system formodifying the adhesive properties of substrates such as polymericmaterials.

SUMMARY OF THE INVENTION

A process has now been developed which allows the surface of a substrateto be functionalised in such a way as to impart adhesive properties tothe surface. The resulting functionalised surface is thus capable ofadhering to a variety of materials. Other surface properties of thesubstrate, such as hydrophobicity, hydrophilicity, oleophobicity,oleophilicity and dispersability, may also be controlled or modifiedusing this process as desired. This process is applicable to a widevariety of substrates, including both organic and inorganic materials.

Accordingly, the present invention provides a process for producing asubstrate having an adhesive surface, which process comprises:

(a) contacting the substrate with a carbene precursor, which carbeneprecursor is a compound of the following formula (I):

wherein:

A is an aryl or heteroaryl ring;

y is 1, 2, 3, 4 or 5;

L_(A) is a single bond, -alk-, -arylene-, -alk-arylene-, -X-alk-,-X-alk-X-, -X-arylene-, X-arylene-X-, -X-alk-arylene-, -alk-X-arylene-,-alk-arylene-X, -X-alk-X-arylene-, -alk-X-arylene-X- or-X-alk-X-arylene-X-, wherein X is N(R″), O, or S and wherein alk isC₁₋₂₀ alkylene which is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl;

W_(A) is a group comprising an adhesive functional group or a groupwhich is a precursor of an adhesive functional group;

R is selected from hydrogen, aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₃₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above;

provided that when R is aryl or heteroaryl, said aryl or heteroaryl maybe unsubstituted or substituted by one, two, three, four or five groups,which groups are independently selected from C₁₋₆ alkyl, aryl, cyano,amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonicacid, sulfonyl and -L_(B)-W_(B), wherein L_(B) is as defined above forL_(A) and is the same as or different from L_(A), and W_(B) is asdefined above for W_(A) and is the same as or different from W_(A); and

(b) either

(i) when W_(A) or W_(B) comprises an adhesive functional group,generating a carbene reactive intermediate from the carbene precursor sothat it reacts with the substrate to functionalise the surface, therebyyielding said substrate having an adhesive surface; or

(ii) when W_(A) or W_(B) comprises a group which is a precursor of anadhesive functional group, generating a carbene reactive intermediatefrom the carbene precursor so that it reacts with the substrate tofunctionalise the surface, and (c) converting said group which is aprecursor into an adhesive functional group thereby yielding saidsubstrate having an adhesive surface.

In step (b), the carbene reactive intermediate is typically generated byelectromagnetic irradiation, ultrasonic irradiation or thermalirradiation. Typically, the carbene reactive intermediate is generatedby thermal irradiation, for instance by heating.

The adhesive functional groups which are introduced onto the surface ofthe substrate by the process of the invention are themselves capable ofinteraction with the surfaces of other materials (termed herein“adherends”), in order to aid adhesion of the substrate to thosematerials. Different adhesive functional groups are capable ofinteraction with different adherends. Thus, by selecting an appropriateadhesive functional group, the substrate in question can be adhered to aparticular adherend as desired.

Furthermore, by selecting an appropriate adhesive functional groupcertain other surface properties of the substrate, includingdispersability, hydrophobicity, hydrophilicity, oleophobicity andoleophilicity, may be modified or controlled as desired.

The process of the invention offers significant economic and technicalbulk advantages. First, it is applicable to a diverse range ofsubstrates including but not limited to natural and synthetic polymersand inorganic solids, and to a diverse range of adherends which may beadhered to such substrates. Second, only the surface of the substrate ismodified: the fact that the functionality is confined to the surface ofthe substrate is advantageous because the bulk of the substrate iseffectively unchanged and therefore the bulk properties of thesubstrate, including mechanical strength, remain unaffected by theadhesive properties that are imparted to its surface. This isparticularly significant for applications in which it is important toretain the properties of the individual materials in a compositematerial formed by adhesion.

The invention further provides a carbene precursor compound of thefollowing formula (I):

wherein:

A is an aryl or heteroaryl ring;

y is 1, 2, 3, 4 or 5;

L_(A) is a single bond, -alk-, -arylene-, -alk-arylene-, -X-alk-,-X-alk-X-, -X-arylene-, X-arylene-X-, -X-alk-arylene-, -alk-X-arylene-,-alk-arylene-X, -X-alk-X-arylene-, -alk-X-arylene-X- or-X-alk-X-arylene-X-, wherein X is N(R″), O, or S and wherein alk isC₁₋₂₀ alkylene which is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl;

W_(A) is a group comprising an adhesive functional group or a groupwhich is a precursor of an adhesive functional group;

R is selected from aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above, provided that R is not CF₃;

provided that when R is aryl or heteroaryl, said aryl or heteroaryl maybe unsubstituted or substituted by one, two, three, four or five groups,which groups are independently selected from C₁₋₆ alkyl, aryl, cyano,amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₄alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀alkylthio, arylthio, sulfonicacid, sulfonyl and -L_(B)-W_(B), wherein L_(B) is as defined above forL_(A) and is the same as or different from L_(A), and W_(B) is asdefined above for W_(A) and is the same as or different from W_(A),

provided that the compound is not:4,4′-bis(N-acetyl-2-aminoethyl)diphenyldiazomethane,1-{2-[4-(diazo-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)phenyl phenyl diazomethane,bis-4,4′-N,N-dimethylamino diphenyldiazomethane,4-([3,4-dimethoxyphenyl]oxymethyl)phenyl phenyl diazomethane,4-([3-N,N-diethylaminophenyl]oxymethyl)phenyl phenyl diazomethane,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)phenyl phenyl diazomethaneor bis-4,4′-tert-butyl ester diphenyldiazomethane.

The present invention further provides a process for producing asubstrate having a functionalised surface, which process comprises: (a)contacting the substrate with a carbene precursor compound of formula(I) as defined above; and (b) generating a carbene reactive intermediatefrom the carbene precursor so that it reacts with the substrate tofunctionalise the surface, thereby yielding said substrate having afunctionalised surface.

The invention further provides a substrate which is obtainable by theprocess of the invention for producing a substrate having an adhesivesurface as defined above. Yet further, the invention provides asubstrate which is obtainable by the process of the invention forproducing a substrate having a functionalised surface as defined above.

The invention further provides a substrate having a functionalisedsurface, which surface is functionalised with one or more groups of thefollowing formula (II):

wherein:

* is the point of attachment of the group of formula (II) to thesubstrate;

A is an aryl or heteroaryl ring;

y is 1, 2, 3, 4 or 5;

L_(A) is a single bond, -alk-, -arylene-, -alk-arylene-, -X-alk-,-X-alk-X-, -X-arylene-, X-arylene-X-, -X-alk-arylene-, -alk-X-arylene-,-alk-arylene-X, -X-alk-X-arylene-, -alk-X-arylene-X- or-X-alk-X-arylene-X-, wherein X is N(R″), O, or S and wherein alk isC₁₋₂₀ alkylene which is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl;

W_(A) is a group comprising a functional group selected from: OH, NH₂,SH, M, a group containing an aliphatic carbon-carbon double bond, agroup containing an epoxide group, and a group having the followingstructure:

X¹ is a single bond, C(R″)(R′″), N(R″) or O, wherein R″ is as definedabove and R′″ is H, C₁₋₆ alkyl or aryl;

Prot is a protecting group which is a precursor to a —CH═CH₂ group;

M is a group that is capable of adhering to a metal, a metal alloy or ametal salt, or M is a group which is a precursor of a group that iscapable of adhering to a metal, metal alloy or a metal salt;

R is selected from hydrogen, aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above;

provided that when R is aryl or heteroaryl, said aryl or heteroaryl maybe unsubstituted or substituted by one, two, three, four or five groups,which groups are independently selected from C₁₋₆ alkyl, aryl, cyano,amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonicacid, sulfonyl and -L_(B)-W_(B), wherein L_(B) is as defined above forL_(A) and is the same as or different from L_(A), and W_(B) is asdefined above for W_(A) and is the same as or different from W_(A).

The point of attachment of the group of formula (II) to the substrate isdepicted “*”. Thus, in the substrate of the invention having afunctionalised surface as defined above, the carbon atom marked “*” isbonded to the substrate. As the skilled person would understand, variousdifferent modes of binding of the group of formula (II) to the substrateare possible via that carbon atom. For example, the bond between thecarbon atom marked “*” and an atom “Z” of the substrate may be a singlecovalent bond, in which case that carbon atom is also bonded to anotheratom (for example a hydrogen atom), as follows:

Alternatively, the bond between the carbon atom marked “*” and an atom“Z” of the substrate may be a double bond, as follows:

Alternatively, the bond between the carbon atom marked “*” and an atom“Z” of the substrate may be a dative bond (also known as a coordinatebond), in which both electrons are provided by the carbon atom, asfollows:

Alternatively, the carbon atom marked “*” of the group of formula (II)may be bonded to two atoms, “Z” and “V”, of the substrate, wherein thebonds between the carbon atom marked “*” and the atoms Z and Z′ are bothsingle bonds, as follows:

The invention further provides a process for producing a compound offormula (III):

wherein:

A is an aryl or heteroaryl ring;

y is 1, 2, 3, 4 or 5;

L_(A) is a single bond, -alk-, -arylene-, -alk-arylene-, -X-alk-,-X-alk-X-, -X-arylene-, X-arylene-X-, -X-alk-arylene-, -alk-X-arylene-,-alk-arylene-X, -X-alk-X-arylene-, -alk-X-arylene-X- or-X-alk-X-arylene-X-, wherein X is N(R″), O, or S and wherein alk isC₁₋₂₀ alkylene which is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl;

W_(A) is a group comprising an adhesive functional group or a groupwhich is a precursor of an adhesive functional group;

R is selected from aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above, provided that R is not CF₃;

provided that when R is aryl or heteroaryl, said aryl or heteroaryl maybe unsubstituted or substituted by one, two, three, four or five groups,which groups are independently selected from C₁₋₆ alkyl, aryl, cyano,amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonicacid, sulfonyl and -L_(B)-W_(B), wherein L_(B) is as defined above forL_(A) and is the same as or different from L_(A), and W_(B) is asdefined above for W_(A) and is the same as or different from W_(A); and

provided that the compound is not:4,4′-bis(N-acetyl-2-aminoethyl)benzophenone hydrazone,1-{2-[4-(hydrazono-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4,4-bis-N,N-dimethylamino benzophenone hydrazone,4-([3,4-dimethoxyphenyl]oxymethyl)benzophenone hydrazone,4-([3-N,N-diethylaminophenyl]oxymethyl)benzophenone hydrazone,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)benzophenone hydrazone or4,4′-bis-tert-butyl ester benzophenone hydrazone;

the process comprising treating a compound of formula (IV) withhydrazine in the presence of heat:

wherein R, A, L_(A), W_(A), and y are as defined above.

The resulting compound of formula (III) may subsequently be convertedinto carbene precursor compounds of formula (I).

Accordingly, the invention further provides a process for producing acarbene precursor compound of formula (I):

wherein R, A, L_(A), W_(A), and y are as defined above for the carbeneprecursor compounds of the invention, which process comprises oxidizinga compound of formula (III) as defined above.

BRIEF DESCRIPTION OF THE FIGURE

FIG. 1 is a bar chart of the results of the AlamarBlue™ cellproliferation study of Example 13, showing the average relativefluorescent unit (RFU) value (y axis), on days 5, 8 and 13, for thecontrol Hybond-N polymer membrane (C), the Hybond-N membranefunctionalised with phosphonic acid (18) and the Hybond-N membranefunctionalised with phosphonic acid calcium salt (19) (x axis). Thecross-hatched bars show the results at day 5, the spotted bars at day 8and the solid bars at day 13.

DETAILED DESCRIPTION OF THE INVENTION

The following substituent definitions apply with respect to thecompounds of formula (I), groups of formula (II) and compounds offormulae (III) and (IV) defined herein, whether they are defined inrelation to the processes, compounds, or substrates of the invention:

A C₁₋₂₀ alkyl group is an unsubstituted or substituted, straight orbranched chain saturated hydrocarbon radical. Typically it is C₁₋₁₀alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl or decyl, or C₁₋₆ alkyl, for example methyl, ethyl, propyl,butyl, pentyl or hexyl, or C₁₋₄ alkyl, for example methyl, ethyl,i-propyl, n-propyl, t-butyl, s-butyl or n-butyl. When an alkyl group issubstituted it typically bears one or more substituents selected fromC₁₋₆ alkyl which is unsubstituted, aryl (as defined herein), cyano,amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino,arylalkylamino, amido, hydroxy, halo, carboxy, ester, keto, C₁₋₆ alkoxy,aryloxy, haloalkyl, sulfonic acid, sulfhydryl (i.e. thiol, —SH),C₁₋₁₀alkylthio, arylthio and sulfonyl. Examples of substituted alkylgroups include haloalkyl, hydroxyalkyl, aminoalkyl, alkoxyallyl andalkaryl groups. The term alkaryl, as used herein, pertains to aC₁₋₂₀alkyl group in which at least one hydrogen atom (e.g., 1, 2, 3) hasbeen replaced with an aryl group. Examples of such groups include, butare not limited to, benzyl (phenylmethyl, PhCH₂—), benzhydryl (Ph₂CH—),trityl (triphenylmethyl, Ph₃C—), phenethyl (phenylethyl, Ph—CH₂CH₂—),styryl (Ph—CH═CH—), cinnamyl (Ph—CH═CH—CH₂—).

A C₃₋₂₀ cycloalkyl group is an unsubstituted or substituted alkyl groupwhich is also a cyclyl group; that is, a monovalent moiety obtained byremoving a hydrogen atom from an alicyclic ring atom of a carbocyclicring of a carbocyclic compound, which moiety has from 3 to 20 carbonatoms (unless otherwise specified), including from 3 to 20 ring atoms.Thus, the term “cycloalkyl” includes the sub-classes cycloalkyenyl andcycloalkynyl. Preferably, each ring has from 3 to 7 ring atoms. Examplesof groups of C₃₋₂₀ cycloalkyl groups include cycloalkyl, C₃₋₁₅cycloalkyl, C₃₋₁₀ cycloalkyl, C₃₋₇ cycloalkyl. When a C₃₋₂₀ cycloalkylgroup is substituted it typically bears one or more substituentsselected from C₁₋₆ alkyl which is unsubstituted, aryl (as definedherein), cyano, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, keto,C₁₋₆ alkoxy, aryloxy, haloalkyl, sulfonic acid, sulfhydryl (i.e. thiol,—SH), C₁₋₁₀ alkylthio, arylthio and sulfonyl.

Examples of C₃₋₂₀ cycloalkyl groups include, but are not limited to,those derived from saturated monocyclic hydrocarbon compounds:

cyclopropane (C₃), cyclobutane (C₄), cyclopentane (C₅), cyclohexane(C₆), cycloheptane (C₇), methylcyclopropane (C₄), dimethylcyclopropane(C₅), methylcyclobutane (C₅), dimethylcyclobutane (C₆),methylcyclopentane (C₆), dimethylcyclopentane (C₇), methylcyclohexane(C₇), dimethylcyclohexane (C₈), menthane (C₁₀);

unsaturated monocyclic hydrocarbon compounds:

cyclopropene (C₃), cyclobutene (C₄), cyclopentene (C₅), cyclohexene(C₆), methylcyclopropene (C₄), dimethylcyclopropene (C₅),methylcyclobutene (C₅), dimethylcyclobutene (C₆), methylcyclopentene(C₆), dimethylcyclopentene (C₇), methylcyclohexene (C₇),dimethylcyclohexene (C₈);

saturated polycyclic hydrocarbon compounds:

thujane (C₁₀), carane (C₁₀), pinane (C₁₀), bornane (C₁₀), norcarane(C₇), norpinane (C₇), norbornane (C₇), adamantane (C₁₀), decalin(decahydronaphthalene) (C₁₀); unsaturated polycyclic hydrocarboncompounds: camphene (C₁₀), limonene (C₁₀), pinene (C₁₀);

polycyclic hydrocarbon compounds having an aromatic ring:

indene (C₉), indane (e.g., 2,3-dihydro-1H-indene) (C₉), tetraline(1,2,3,4-tetrahydronaphthalene) (C₁₀), acenaphthene (C₁₂), fluorene(C₁₃), phenalene (C₁₃), acephenanthrene (C₁₅), aceanthrene (C₁₆),cholanthrene (C₂₀).

A C₃₋₂₀ heterocyclyl group is an unsubstituted or substituted monovalentmoiety obtained by removing a hydrogen atom from a ring atom of aheterocyclic compound, which moiety has from 3 to 20 ring atoms (unlessotherwise specified), of which from 1 to 10 are ring heteroatoms.Preferably, each ring has from 3 to 7 ring atoms, of which from 1 to 4are ring heteroatoms. When a C₃₋₂₀ heterocyclyl group is substituted ittypically bears one or more substituents selected from C₁₋₆ alkyl whichis unsubstituted, aryl (as defined herein), cyano, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, hydroxy, halo, carboxy, ester, keto, C₁₋₆ alkoxy, aryloxy,haloalkyl, sulfonic acid, sulfhydryl (i.e. thiol, —SH), C₁₋₁₀ alkylthio,arylthio and sulfonyl.

Examples of groups of heterocyclyl groups include C₃₋₂₀heterocyclyl,C₅₋₂₀heterocyclyl, C₃₋₁₅heterocyclyl, C₅₋₁₅heterocyclyl,C₃₋₁₂heterocyclyl, C₅₋₁₂heterocyclyl, C₃₋₁₀heterocyclyl,C₅₋₁₀heterocyclyl, C₃₋₇heterocyclyl, C₅₋₇heterocyclyl, andC₅₋₆heterocyclyl.

Examples of (non-aromatic) monocyclic C₃₋₂₀ heterocyclyl groups include,but are not limited to, those derived from:

N₁: aziridine (C₃), azetidine (C₄), pyrrolidine (tetrahydropyrrole)(C₅), pyrroline (e.g., 3-pyrroline, 2,5-dihydropyrrole) (C₅), 2H-pyrroleor 3H-pyrrole (isopyrrole, isoazole) (C₅), piperidine (C₆),dihydropyridine (C₆), tetrahydropyridine (C₆), azepine (C₇);

O₁: oxirane (C₃), oxetane (C₄), oxolane (tetrahydrofuran) (C₅), oxole(dihydrofuran) (C₅), oxane (tetrahydropyran) (C₆), dihydropyran (C₆),pyran (C₆), oxepin (C₇);

S₁: thiirane (C₃), thietane (C₄), thiolane (tetrahydrothiophene) (C₅),thiane (tetrahydrothiopyran) (C₆), thiepane (C₇);

O₂: dioxolane (C₅), dioxane (C₆), and dioxepane (C₇);

O₃: trioxane (C₆);

N₂: imidazolidine (C₅), pyrazolidine (diazolidine) (C₅), imidazoline(C₅), pyrazoline (dihydropyrazole) (C₅), piperazine (C₆);

N₁O₁: tetrahydrooxazole (C₅), dihydrooxazole (C₅), tetrahydroisoxazole(C₅), dihydroisoxazole (C₅), morpholine (C₆), tetrahydrooxazine (C₆),dihydrooxazine (C₆), oxazine (C₆);

N₁S₁: thiazoline (C₅), thiazolidine (C₅), thiomorpholine (C₆);

N₂O₁: oxadiazine (C₆);

O₁S₁: oxathiole (C₅) and oxathiane (thioxane) (C₆); and,

N₁O₁S₁: oxathiazine (C₆).

Examples of C₃₋₂₀ heterocyclyl groups which are also aryl groups aredescribed below as heteroaryl groups.

An aryl group is a substituted or unsubstituted, monocyclic or bicyclicaromatic group which typically contains from 6 to 14 carbon atoms,preferably from 6 to 10 carbon atoms in the ring portion. Examplesinclude phenyl, naphthyl, indenyl and indanyl groups. An aryl group isunsubstituted or substituted. When an aryl group as defined above issubstituted it typically bears one or more substituents selected fromC₁-C₆ alkyl which is unsubstituted (to form an aralkyl group), arylwhich is unsubstituted, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,hydroxy, halo, carboxy, ester, keto, alkoxy, aryloxy, haloalkyl,sulfhydryl (i.e. thiol, —SH), C₁₋₁₀ alkylthio, arylthio, sulfonic acidand sulfonyl. Typically it carries 0, 1, 2 or 3 substituents. The termaralkyl as used herein, pertains to an aryl group in which at least onehydrogen atom (e.g., 1, 2, 3) has been substituted with a C₁₋₆ alkylgroup. Examples of such groups include, but are not limited to, tolyl(from toluene), xylyl (from xylene), mesityl (from mesitylene), andcumenyl (or cumyl, from cumene), and duryl (from durene).

Alternatively, the ring atoms may include one or more heteroatoms, as ina heteroaryl group. A heteroaryl group is a substituted or unsubstitutedmono- or bicyclic heteroaromatic group which typically contains from 6to 10 atoms in the ring portion including one or more heteroatoms. It isgenerally a 5- or 6-membered ring, containing at least one heteroatomselected from O, S, N, P, Se and Si. It may contain, for example, 1, 2or 3 heteroatoms. Examples of heteroaryl groups include pyridyl,pyrazinyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, pyrazolidinyl,pyrrolyl, oxazolyl, oxadiazolyl, isoxazolyl, thiadiazolyl, thiazolyl,isothiazolyl, imidazolyl, pyrazolyl, quinolyl and isoquinolyl. Aheteroaryl group may be unsubstituted or substituted, for instance, asspecified above for aryl. Typically it carries 0, 1, 2 or 3substituents.

A C₁₋₂₀ alkylene group is an unsubstituted or substituted bidentatemoiety obtained by removing two hydrogen atoms, either both from thesame carbon atom, or one from each of two different carbon atoms, of ahydrocarbon compound having from 1 to 20 carbon atoms (unless otherwisespecified), which may be aliphatic or alicyclic, and which may besaturated, partially unsaturated, or fully unsaturated. Thus, the term“alkylene” includes the sub-classes alkenylene, alkynylene,cycloalkylene, etc., discussed below. Typically it is C₁₋₁₀ alkylene,for instance C₁₋₆ alkylene. Preferably it is C₁₋₄ alkylene, for examplemethylene, ethylene, i-propylene, n-propylene, t-butylene, s-butylene orn-butylene. It may also be pentylene, hexylene, heptylene, octylene andthe various branched chain isomers thereof. An alkylene group may beunsubstituted or substituted as specified above for alkyl.

In this context, the prefixes (e.g., C₁₋₄, C₁₋₇, C₁₋₂₀, C₂₋₇, C₃₋₇,etc.) denote the number of carbon atoms, or range of number of carbonatoms. For example, the term “C₁₋₄alkylene,” as used herein, pertains toan alkylene group having from 1 to 4 carbon atoms. Examples of groups ofalkylene groups include C₁₋₄ alkylene (“lower alkylene”), C₁₋₇ alkylene,C₁₋₁₀ alkylene and C₁₋₂₀ alkylene.

Examples of linear saturated C₁₋₇ alkylene groups include, but are notlimited to, —(CH₂)_(n)— where n is an integer from 1 to 7, for example,—CH₂-(methylene), —CH₂CH₂-(ethylene), —CH₂CH₂CH₂-(propylene), and—CH₂CH₂CH₂CH₂-(butylene).

Examples of branched saturated C₁₋₇ alkylene groups include, but are notlimited to, —CH(CH₃)—, —CH(CH₃)CH₂—, —CH(CH₃)CH₂CH₂—,—CH(CH₃)CH₂CH₂CH₂—, —CH₂CH(CH₃)CH₂—, —CH₂CH(CH₃)CH₂CH₂—, —CH(CH₂CH₃)—,—CH(CH₂CH₃)CH₂—, and —CH₂CH(CH₂CH₃)CH₂—.

Examples of linear partially unsaturated C₁₋₇ alkylene groups include,but is not limited to, —CH═CH— (vinylene), —CH═CH—CH₂—, —CH₂—CH═CH₂—,—CH═CH—CH₂—CH₂—, —CH═CH—CH₂—CH₂—CH₂—, —CH═CH—CH═CH—, —CH═CH—CH═CH—CH₂—,—CH═CH—CH═CH—CH₂—CH₂—, —CH═CH—CH₂—CH═CH—, and —CH═CH—CH₂—CH₂—CH═CH—.

Examples of branched partially unsaturated C₁₋₇ alkylene groups include,but is not limited to, —C(CH₃)═CH—, —C(CH₃)═CH—CH₂—, and—CH═CH—CH(CH₃)—.

Examples of alicyclic saturated C₁₋₇ alkylene groups include, but arenot limited to, cyclopentylene (e.g., cyclopent-1,3-ylene), andcyclohexylene (e.g., cyclohex-1,4-ylene).

Examples of alicyclic partially unsaturated C₁₋₇ alkylene groupsinclude, but are not limited to, cyclopentenylene (e.g.,4-cyclopenten-1,3-ylene), cyclohexenylene (e.g., 2-cyclohexen-1,4-ylene;3-cyclohexen-1,2-ylene; 2,5-cyclohexadien-1,4-ylene).

An arylene group is an unsubstituted or substituted bidentate moietyobtained by removing two hydrogen atoms, one from each of two differentaromatic-ring atoms of an aromatic compound, which moiety has from 5 to14 ring atoms (unless otherwise specified). Typically, each ring hasfrom 5 to 7 or from 5 to 6 ring atoms. An arylene group may beunsubstituted or substituted, for instance, as specified above for aryl.

In this context, the prefixes (e.g., C₅₋₂₀, C₆₋₂₀, C₅₋₁₄, C₅₋₇, C₅₋₆,etc.) denote the number of ring atoms, or range of number of ring atoms,whether carbon atoms or heteroatoms. For example, the term “C₅₋₆arylene,” as used herein, pertains to an arylene group having 5 or 6ring atoms. Examples of groups of arylene groups include C₅₋₂₀ arylene,C₆₋₂₀ arylene, C₅₋₁₄ arylene, C₆₋₁₄ arylene, C₆₋₁₀ arylene, C₅₋₁₂arylene, C₅₋₁₀ arylene, C₅₋₇ arylene, C₅₋₆ arylene, C₅ arylene, and C₆arylene.

The ring atoms may be all carbon atoms, as in “carboarylene groups”(e.g., C₆₋₂₀ carboarylene, C₆₋₁₄ carboarylene or C₆₋₁₀ carboarylene).

Examples of C₆₋₂₀ arylene groups which do not have ring heteroatoms(i.e., C₆₋₂₀ carboarylene groups) include, but are not limited to, thosederived from the compounds discussed above in regard to aryl groups,e.g. phenylene, and also include those derived from aryl groups whichare bonded together, e.g. phenylene-phenylene (diphenylene) andphenylene-phenylene-phenylene (triphenylene).

Alternatively, the ring atoms may include one or more heteroatoms, as in“heteroarylene groups” (e.g., C₅₋₁₀ heteroarylene).

Examples of C₅₋₁₀ heteroarylene groups include, but are not limited to,those derived from the compounds discussed above in regard to heteroarylgroups.

As used herein the term ester (or carboxylate, carboxylic acid ester oroxycarbonyl) represents a group of formula: —CH))OR, wherein R is anester substituent, for example, a C₁₋₆ alkyl group, a C₃₋₂₀ heterocyclylgroup, or an aryl group (typically a phenyl group). Examples of estergroups include, but are not limited to, —C(═O)OCH₃, —C(═O)OCH₂CH₃,—C(═O)OC(CH₃)₃, and —C(═O)OPh.

As used herein the term amino represents a group of formula —NH₂. Theterm C₁₋₁₀ alkylamino represents a group of formula —NHR′ wherein R′ isa C₁₋₁₀ alkyl group, preferably a C₁₋₆ alkyl group, as definedpreviously. The term di(C₁₋₁₀)alkylamino represents a group of formula—NR′R″ wherein R′ and R″ are the same or different and represent C₁₋₁₀alkyl groups, preferably C₁₋₆ alkyl groups, as defined previously. Theterm arylamino represents a group of formula —NHR′ wherein R′ is an arylgroup, preferably a phenyl group, as defined previously. The termdiarylamino represents a group of formula —NR′R″ wherein W and R″ arethe same or different and represent aryl groups, preferably phenylgroups, as defined previously. The term arylalkylamino represents agroup of formula —NR′R″ wherein R′ is a C₁₋₁₀ alkyl group, preferably aC₁₋₆ alkyl group, and R″ is an aryl group, preferably a phenyl group.

A C₁₋₁₀ alkylthio group is a said C₁₋₁₀ alkyl group, preferably a C₁₋₆alkyl group, attached to a thio group. An arylthio group is an arylgroup, preferably a phenyl group, attached to a thio group.

A C₁₋₁₀ alkoxy group is a said C₁₋₁₀ alkyl group attached to an oxygenatom. A C₁₋₆ alkoxy group is a said C₁₋₆ alkyl group attached to anoxygen atom. A C₁₋₄ alkoxy group is a C₁₋₄ alkyl group attached to anoxygen atom. Examples of C₁₋₄ alkoxy groups include, —OMe (methoxy),—OEt (ethoxy), —O(nPr) (n-propoxy), —O(iPr) (isopropoxy), —O(nBu)(n-butoxy), —O(sBu) (sec-butoxy), —O(iBu) (isobutoxy), and —O(tBu)(tert-butoxy). An aryloxy group is an aryl group, preferably a phenylgroup, attached to an oxygen atom. An example of an aryloxy group is—OPh (phenoxy).

As used herein, the term “phosphonic acid” represents a group of theformula: —P(═O)(OH)₂. As would be understood by the skilled person, aphosphonic acid group (for instance, when employed in the presentinvention as an adhesive functional group) can exist in protonated anddeprotonated forms (for example, —P(═O)(OH)₂, —P(O)(O⁻)₂ and—P(═O)(OH)(O⁻)), and in salt forms (for example, —[P(═O)(OH)(O⁻)]X⁺,—[P(═O)(O⁻)₂]2X⁺ or —[P(═O)(O⁻)₂]Z²⁺, wherein X⁺ is a monovalent cationand Z²⁺ is a dication). Typically, X⁺ is an alkali metal cation or acationic alkaline earth metal monohydroxide. Thus, X⁺ may be Na⁺, K⁺,[CaOH]⁺ or [MgOH]⁺, for instance. Typically, X⁺ is [CaOH]⁺. Typically,Z²⁺ is an alkaline earth metal dication. Thus, Z²⁺ may be Ca²⁺ or Mg²⁺,for example. Typically, Z²⁺ is Ca²⁺.

As used herein, the term “sulfonic acid” represents a group of theformula: —S(═O)₂OH. As would be understood by the skilled person, asulfonic acid group (for instance, when employed in the presentinvention as an adhesive functional group) can exist in protonated anddeprotonated forms (for example, —S(═O)₂OH and —S(═O)₂O⁻), and in saltforms (for example, —S(═O)₂O⁻X⁺, wherein X⁺ is a monovalent cation).Typically, X⁺ is an alkali metal cation or a cationic alkaline earthmetal monohydroxide. Thus, X⁺ may be Na⁺, K⁺, [CaOH]⁺ or [MgOH]⁺, forinstance.

As used herein, the terms “carboxy”, “carboxyl” and “carboxylic acid”each represent a group of the formula: —C(═O)OH, or —COOH. As would beunderstood by the skilled person, a carboxylic acid group (for instance,when employed in the present invention as an adhesive functional group)can exist in protonated and deprotonated forms (for example, —C(═O)OHand —C(═O)O⁻), and in salt forms (for example, —C(═O)O⁻X⁺, wherein X⁺ isa monovalent cation). Typically, X⁺ is an alkali metal cation or acationic alkaline earth metal monohydroxide. Thus, X⁺ may be Na⁺, K⁺,[CaOH]⁺ or [MgOH]⁺, for instance.

As used herein, the term “carboxyl amide” represents a group of formula:—C(O)NH₂.

As used herein, the term “sulfonamide” represents a group of formula:—S(O)₂NH₂.

C₁₋₂₀ alkylene and C₁₋₂₀ alkyl groups as defined herein are eitheruninterrupted or interrupted by one or more heteroatoms or heterogroups,such as S, O or N(R″) wherein R″is H, C₁₋₆ alkyl or aryl (typicallyphenyl), or by one or more arylene (typically phenylene) groups. Thephrase “optionally interrupted” as used herein thus refers to a C₁₋₂₀alkyl group or an alkylene group, as defined above, which isuninterrupted or which is interrupted between adjacent carbon atoms by aheteroatom such as oxygen or sulfur, by a heterogroup such as N(R″)wherein R″ is H, aryl or C₁-C₆ alkyl, or by an arylene group. Forinstance, a C₁₋₂₀ alkyl group such as n-butyl may be interrupted by theheterogroup N(R″) as follows: —CH₂N(R″)CH₂CH₂CH₃, —CH₂CH₂N(R″)CH₂CH₃, or—CH₂CH₂CH₂N(R″)CH₃. Similarly, an alkylene group such as n-butylene maybe interrupted by the heterogroup N(R″) as follows: —CH₂N(R″)CH₂CH₂CH₂—,—CH₂CH₂N(R″)CH₂CH₂—, or —CH₂CH₂CH₂N(R″)CH₂—.

Unless otherwise specified, included in the above are the well knownionic, salt, and solvate forms of those substituents. For example, areference to carboxylic acid, carboxy or carboxyl group (or the formulae—COOH or —C(═O)OH) also includes the anionic (carboxylate) form (—COO⁻),a salt or solvate thereof. Similarly, a reference to an amino groupincludes the protonated form (—N⁺HR¹R²), a salt or solvate of the aminogroup, for example, a hydrochloride salt. Similarly, a reference to ahydroxyl group also includes the anionic form (—O⁻), or salt or solvatethereof.

The term “Prot” as used herein, means a protecting group which is aprecursor to a —CH═CH₂ group. Thus, Prot is any protecting group whichis capable of being converted into a —CH═CH₂ group by chemical reaction,or any protecting group for which a —CH═CH₂ group can be substituted bychemical reaction. Examples of protecting groups “Prot” which areprecursors to —CH═CH₂ include 7-oxabicyclo[2.2.1]hept-2-yl;organometallic groups, for instance iron- or cobalt-containingorganometallic groups; and 1,2-dioxygenated substrates. Typically, Protis 7-oxabicyclo[2.2.1]hept-2-yl. When Prot is7-oxabicyclo[2.2.1]hept-2-yl, the group —O—C(═O)-Prot is readilyconverted into the group —O—C(30)—CH═CH₂ by heating (see Example 4below).

The invention provides a process for producing a substrate having anadhesive surface. The term “adhesive surface”, as used herein, refers toa surface of the substrate which is capable of acting as an adhesive. Asurface of the substrate which is capable of acting as an adhesive isone which is capable of attachment to the surface of another material,which may be known as an “adherend”, such that the substrate and theadherend are held together.

Without wishing to be bound by theory, the attachment of the adhesivesurface to the surface of the adherend may be through a physicalinteraction between the adhesive surface and the adherend (e.g. due toan electrostatic attraction between adhesive and adherend, or anattraction owing to their mutual solubility), through a mechanicalinteraction between adhesive surface and adherend (e.g. due tomechanical interlocking) or through the formation of chemical bondsbetween adhesive surface and adherend (e.g. covalent bonds, ionic bonds,hydrogen bonds or other non-covalent bonds).

In the carbene precursor compound of formula (I), used in the processfor producing a substrate having an adhesive surface, W_(A) and, wherepresent, W_(B) are groups comprising either (i) an adhesive functionalgroup, or (ii) a group which is a precursor of an adhesive functionalgroup.

The term “adhesive functional group”, as used herein, refers to afunctional group which is capable of interaction with the surface of anadherend, in order to facilitate adhesion of the substrate to theadherend. Certain types of adhesive functional groups are capable ofinteracting with certain types of adherend by forming covalent ornon-covalent chemical bonds, or “cross links”, to those adherends. Thus,typically, a covalent bond is formed or a non-covalent interactionoccurs between the adhesive functional group and the surface of theadherend. Examples of non-covalent interactions are electrostatic orionic interactions, hydrogen bonding and Van der Waals forces. In oneembodiment, the term “adhesive functional group” is a group which iscapable of forming a covalent or non-covalent chemical interaction withan adherend. In another embodiment, the term “adhesive functional group”is a group which is capable of forming a covalent or ionic interactionwith an adherend. The mechanisms of formation of chemical bonds betweenadhesive functional group and adherend include free radical crosslinking, ionic cross linking and nucleophilic cross linking. Typically,adhesive functional groups such as hydroxyl, amino and thiol are usedfor nucleophilic cross linking and ionic cross linking reactions,whereas groups comprising aliphatic carbon-carbon double bonds aretypically used for free radical cross linking.

Certain types of adhesive functional groups are capable of interactionwith certain types of adherends, in order to aid adhesion of thesubstrate to those adherends. Thus, by selecting an appropriate adhesivefunctional group, the substrate in question can be adhered to aparticular adherend as desired.

Some adhesive functional groups are capable of modifying certain surfaceproperties of the substrate including dispersability, hydrophobicity,hydrophilicity, oleophobicity and oleophilicity. An adhesive functionalgroup may for instance interact with a particular solvent in such a waythat it imparts a particular dispersability in that solvent to thesubstrate. Similarly, an adhesive functional group may interact withwater in such a way that it imparts a particular hydrophilicity orhydrophobicity to the substrate. Thus, by selecting an appropriateadhesive functional group, the dispersability, hyrophobicity,hydrophilicity, oleophobicity and/or oleophilicity of the substrate canbe controlled as desired.

Accordingly, in one embodiment of the process of the invention forproducing a substrate having an adhesive surface, the process issuitable for producing a substrate which has a desirable dispersability,hydrophobicity, hydrophilicity, oleophobicity and/or oleophilicity.

Adhesive functional groups which may be employed in the presentinvention include OH, NH₂ and SH. Accordingly, W_(A) or W_(B) istypically a group which comprises at least one OH, NH₂ or SH group.Thus, W_(A) or W_(B) can be a single OH, NH₂ or SH group, or a groupwhich contains a plurality of OH, NH₂ or SH moieties. Thus W_(A) orW_(B) may be a polyol, polythiol or a group containing a plurality ofamino groups. Typically, W_(A) or W_(B) is -L²-OH, -L²-NH₂, -L²-SH,C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl,wherein said C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl andheteroaryl are each substituted by -L²-OH, -L²-NH₂ or -L²-SH, whereinsaid C₁₋₂₀ alkyl is optionally interrupted by N(R″), O, S or arylene,wherein R″ is H, C₁₋₆ alkyl or aryl, and wherein L² is a single bond,C₁₋₆ alkylene, arylene, -arylene-C₁₋₆ alkylene- or -C₁₋₆alkylene-arylene-, wherein each of said C₁₋₆ alkylene groups isoptionally interrupted by N(R″), O, S or arylene. Thus, in oneembodiment, W_(A) or W_(B) is a group of the following structure:

in which each R⁴, which may be the same or different, is OH, NH₂ or SH.Such groups comprising hydroxyl, amino or thiol adhesive functionalgroups may be used for nucleophilic cross linking and ionic crosslinking reactions. Thus, hydroxyl, amino or thiol adhesive functionalgroups may be used for adhering a substrate to an adherend comprising anunsaturated bond (for instance an adherend which is or comprises analkene, alkyne or an enol ether) or to an adherend which comprises analkyl halide, epoxide, alkyl tosylate or equivalent functionality. Suchequivalent functionalities would be apparent to one skilled in the art.

Another adhesive functional group which may be employed in the presentinvention is a group containing an aliphatic carbon-carbon double bond.Accordingly, W_(A) or W_(B) is typically a group which comprises atleast one aliphatic carbon-carbon double pond. Thus, W_(A) or W_(B) canbe a group which comprises a single aliphatic carbon-carbon double bond,such as a vinyl group, an acrylonitrile group or an acrylate group, orcan be a group which comprises a plurality of aliphatic carbon-carbondouble bonds. Thus W_(A) or W_(B) may be, or comprise, a polyene, forexample a group derived from vinyl norbornene or ethylidene norbornene.W_(A) or W_(B) may be a group which comprises one or more groups of thefollowing structure:

wherein:

R¹, R² and R³, which may be the same or different, are each selectedfrom H, C₁₋₆ alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio andarylthio. Typically, R¹ is H or cyano. Typically, R² and R³ areindependently selected from H, C₁₋₆ alkyl and aryl. More typically, R²and R³ are each H. Typically, W_(A) or W_(B) is

C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl,wherein said C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl andheteroaryl are each substituted by:

wherein R¹, R² and R³ are as defined above, wherein said C₁₋₂₀ alkyl isoptionally interrupted by N(R″), O, S or arylene, wherein R″ is H, C₁₋₆alkyl or aryl, and wherein L² is a single bond, C₁₋₆ alkylene, arylene,arylene-C₁₋₆ alkylene- or —C₁₋₆ alkylene-arylene-, wherein each of saidC₁₋₆ alkylene groups is optionally interrupted by N(R″), O, S orarylene. Such groups comprising one or more aliphatic carbon-carbondouble bonds may be used for free radical cross linking reactions, inorder to adhere a substrate to radicals, including carbon-centred andheteroatom-centred (for example, O-, N- or S-centred) radicals. Suchgroups may also be used for coupling a substrate to an adherend underionic conditions, in cases where the adherend includes an electrophilicunit such as a carbocation, or a nucleophilic atom such as O, N or S.

W_(A) or W_(B) may be a group which comprises one or more groups of thefollowing structure:

in which X′ is a single bond, O, C(R″)(R′″) or N(R″), wherein R″ and R′″are independently selected from H, C₁₋₆ alkyl or aryl, and R¹, R² andR³, which may be the same or different, are each selected from H, C₁₋₆alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, halo, carboxy, ester,C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio and arylthio. Typically, R′ is Hor cyano. Typically, R² and R³ are independently selected from H, C₁₋₆alkyl and aryl. More typically, R² and R³ are each H. Typically, W_(A)or W_(B) is:

C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl,wherein said C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl andheteroaryl are each substituted by:

wherein X¹, R¹, R² and R³ are as defined above, wherein said C₁₋₂₀ allylis optionally interrupted by N(R″), O, S or arylene, wherein R″ is H,C₁₋₆ alkyl or aryl, and wherein L² is a single bond, C₁₋₆ alkylene,arylene, -arylene-C₁₋₆ alkylene- or C₁₋₆ alkylene-arylene-, wherein eachof said C₁₋₆ alkylene groups is optionally interrupted by N(R″), O, S orarylene. Such groups may be used for free radical cross linkingreactions, in order to adhere a substrate to radicals, includingcarbon-centred and heteroatom-centred (for example, O-, N- or S-centred)radicals. Such groups may also be used for coupling a substrate to anadherend under ionic conditions, in cases where the adherend includes anucleophilic atom such as O, N or S. In addition where X¹ is O, suchgroups may be used specifically for acrylate coating adhesion.

Another adhesive functional group which may be employed in the presentinvention is an epoxide group. Accordingly, W_(A) or W_(B) is typicallya group which comprises at least one epoxide group. Thus, W_(A) or W_(B)can be a group which comprises a single epoxide group, or a group whichcomprises a plurality of epoxide groups. W_(A) or W_(B) may be a groupwhich comprises one or more groups of the following structure:

in which R¹, R² and R³, which may be the same or different, are eachselected from H, C₁₋₆ alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio andarylthio. Typically, R¹, R² and R³ are independently selected from H,C₁₋₆ alkyl and aryl. More typically, R¹, R² and R³ are each H.Typically, W_(A) or W_(B) is

C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl,wherein said C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl andheteroaryl are each substituted by

wherein said C₁₋₂₀ alkyl is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl, and wherein R¹, R² and R³are as defined above and L² is a single bond, C₁₋₆ alkylene, arylene,-arylene-C₁₋₆ alkylene- or -C₁₋₆ alkylene-arylene-, wherein each of saidC₁₋₆ alkylene groups is optionally interrupted by N(R″), O, S or arylenewherein R″ is as defined above. Such groups comprising one or moreepoxide groups may be used for nucleophilic cross linking reactionsoperated under acidic or basic conditions, in order to adhere asubstrate to an adherend which comprises a group that includes anucleophilic atom such as O, N or S, or to an adherend which comprisesanother nucleophilic species such as a carbanion (or an organometallicderivative of a carbanion) or an enolate (or an equivalent of anenolate).

Another adhesive functional group which may be employed in the presentinvention is a group that is capable of adhering to a metal or a metalalloy. Yet another adhesive functional group which may be employed inthe present invention is a group that is capable of adhering to a metalion or a metal salt. Accordingly, W_(A) or W_(B) is typically a groupwhich comprises at least one group, denoted “M”, that is capable ofadhering either to a metal, a metal alloy, or a metal ion or salt. Thus,W_(A) or W_(B) can be a group which comprises a single “M” group or agroup which comprises a plurality of “M” groups. Typically, W_(A) orW_(B) is -L²-M, C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, arylor heteroaryl, wherein said C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀heterocyclyl, aryl and heteroaryl are each substituted by -L²-M, whereinsaid C₁₋₂₀ alkyl is optionally interrupted by N(R″), O, S or arylene,wherein R″ is H, C₁₋₆ alkyl or aryl, and wherein L² is a single bond,C₁₋₆ alkylene, arylene, -arylene-C₁₋₆ alkylene- or —C₁₋₆alkylene-arylene-, wherein each of said C₁₋₆ alkylene groups isoptionally interrupted by N(R″), O, S or arylene and M is as definedabove. The groups “M” that are capable of adhering either to a metal, ametal alloy, metal ion or salt are typically used in order to adhere asubstrate to a metal salt, a metal other than an alkali metal or analkaline earth metal, or an alloy of any metal other than an alkalimetal or an alkaline earth metal. Typically, the metal salt is a calciumsalt. Typically, the metal other than an alkali metal or an alkalineearth metal or alloy is selected from: Al, Cu, Pb, Au, Ag, Pt, Pd, Sn,Pb and alloys of those metals. The metal may also include group IV(group 14) elements, for example Ge, Si, Pb and C and alloys of thoseelements. The metallisation of polymer surfaces of relevance in printedcircuit board and electronic technology. Thus, adhesion of such metalsor alloys to substrates may be of use to the electronics industry, forexample in the manufacture of printed circuit boards.

Typically, M is a group comprising one or more phosphonic acid groups.Accordingly, W_(A) or W_(B) is typically a group which comprises atleast one phosphonic acid group. Thus, W_(A) or W_(B) can be a groupwhich comprises a single phosphonic acid group, or a group whichcomprises a plurality of phosphonic acid groups, such as abis-phosphonic acid group or a polyphosphonic acid group. Suitable Mgroups include P(═O)(OH)₂ and

wherein Y is H, C₁₋₆ alkyl, aryl, —OH, —SH or NH₂. Typically, W_(A) orW_(B) is -L²-P(═O)(OH)₂, C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀heterocyclyl, aryl or heteroaryl, wherein said C₁₋₂₀ alkyl, C₃₋₂₀cycloalkyl, C₃₋₂₀ heterocyclyl, aryl and heteroaryl are each substitutedby -L²-P(═O)(OH)₂, wherein said C₁₋₂₀ alkyl is optionally interrupted byN(R″), O, S or arylene, and wherein L² is a single bond, C₁₋₆ alkylene,arylene, -arylene-C₁₋₄ alkylene- or —C₁₋₆ alkylene-arylene-, whereineach of said C₁₋₆ alkylene groups is optionally interrupted by N(R″), O,S or arylene. Groups comprising phosphonic acid moieties may be used formetal adhesion, or for adhesion through an ion exchange reaction or anionic cross linking reaction.

Alternatively, M is a group comprising one or more sulfonic acid groups.Accordingly, W_(A) or W_(B) is typically a group which comprises atleast one sulfonic acid group. Thus, W_(A) or W_(B) can be a group whichcomprises a single sulfonic acid group, or a group which comprises aplurality of sulfonic acid groups, such as a bis-sulfonic acid group ora polysulfonic acid group. Suitable M groups include —S(═O)₂(OH) and—CY[S(O)₂(OH)]₂, wherein Y is H, C₁₋₆ alkyl, aryl, —OH, —SH or NH₂.Typically, W_(A) or WS is -L²-S(═O)₂(OH), C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl,C₃₋₂₀ heterocyclyl, aryl or heteroaryl, wherein said C₁₋₂₀ alkyl, C₃₋₂₀cycloalkyl, C₃₋₂₀ heterocyclyl, aryl and heteroaryl are each substitutedby -L²-S(═O)₂(OH), wherein said C₁₋₂₀ alkyl is optionally interrupted byN(R″), O, S or arylene, and wherein L² is a single bond, C₁₋₆ alkylene,arylene, -arylene-C₁₋₆ alkylene- or —C₁₋₆ alkylene-arylene-, whereineach of said C₁₋₆ alkylene groups is optionally interrupted by N(R″), O,S or arylene. Groups comprising sulfonic acid moieties may be used formetal adhesion, or for adhesion through an ion exchange reaction or anionic cross linking reaction.

Alternatively, M is a group comprising one or more carboxylic acidgroups. Accordingly, W_(A) or W_(B) is typically a group which comprisesat least one carboxylic acid group. Thus, W_(A) or W_(B) can be a groupwhich comprises a single carboxylic acid group, or a group whichcomprises a plurality of carboxylic acid groups, such as abis-carboxylic acid group or a polycarboxylic acid group. Suitable Mgroups include —C(═O)OH and —CY(COOH)₂, wherein Y is H, C₁₋₆ alkyl,aryl, —OH, —SH or NH₂. Typically, W_(A) or W_(B) is -L²-COOH, C₁₋₂₀alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl, whereinsaid C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl andheteroaryl are each substituted by -L²-COOH, wherein said C₁₋₂₀ alkyl isoptionally interrupted by N(R″), O, S or arylene, and wherein L² is asingle bond, C₁₋₆ alkylene, arylene, -arylene-C₁₋₆ alkylene- or —C₁₋₆alkylene-arylene-, wherein each of said C₁₋₆ alkylene groups isoptionally interrupted by N(R″), O, S or arylene. Groups comprisingcarboxylic acid moieties may be used for metal adhesion, or for adhesionthrough an ion exchange reaction or anionic cross-linking reaction.

The adhesive functional groups defined in the preceding paragraphs,which comprise one or more phosphonic acid, sulfonic acid or carboxylicacid groups, can be used for adhesion of the substrate to biologicalcells or tissue. Adhering a substrate to cells or tissue is of use intissue engineering applications, applications involving cell culturesand other medical applications. Without wishing to be bound by theory,it is thought that the acidic adhesive functional groups serve to modifythe free energy of the surface of the substrate so that the surface ismore hydrophilic. That increased hydrophilicity makes the substrate morebiocompatible and thus more attractive to biological tissue and cells.This promotes adhesion of the substrate to cells or tissue.

Adhesion of the substrate to cells or tissue is typically enhanced ifthe phosphonic acid, sulfonic acid or carboxylic acid group is presentin the form of a salt with a metal counterion, particularly in the formof a calcium salt. Accordingly, in one embodiment W_(A) or W_(B)comprises a group which is a salt of a phosphonic acid group, a salt ofa sulfonic acid group or a salt of a carboxylic acid group. Typically,the salt is a calcium salt. Accordingly, W_(A) or W_(B) may comprise agroup which is a calcium salt of a phosphonic acid group, a calcium saltof a sulfonic acid group or a calcium salt of a carboxylic acid group.More typically, W_(A) or W_(B) comprises a group which is a calcium saltof a phosphonic acid group. The use of calcium salts of phosphonic,sulfonic or carboxylic acid group can achieve enhanced adhesion of thesubstrate to cells or tissue compared with the use of the correspondingfree acid groups. Suitable groups “M” as defined above thus includesalts, typically calcium salts, of groups of any of the followingstructures: —P(═O)(OH)₂; —C(Y)[P(═O)(OH)₂]₂; —C(═O)OH; —CY(COOH)₂;—S(O)₂OH and —CY[S(═O)₂OH]₂, wherein Y is H, C₁₋₆ alkyl, aryl, —OH,

—SH or NH₂. Accordingly, W_(A) or W_(B) is typically -L²-M, C₁₋₂₀ alkyl,C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl, wherein saidC₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl and heteroarylare each substituted by -L²-M; wherein said C₁₋₂₀ alkyl is optionallyinterrupted by N(R″), O, S or arylene; wherein L² is a single bond, C₁₋₆alkylene, arylene, -arylene-C₁₋₆ alkylene- or —C₁₋₆ alkylene-arylene-;wherein each of said C₁₋₆ alkylene groups is optionally interrupted byN(R″), O, S or arylene; and wherein M is selected from a salt, typicallya calcium salt, of a group having any one of the following structures:—P(═O)(OH)₂; —C(Y)[P(═O)(OH)₂]₂; —C(═O)OH; —CY(COOH)₂; —S(O)₂OH and—CY[S(═O)₂OH]₂, wherein Y is H, C₁₋₆ alkyl, aryl, —OH, —SH or NH₂.Typically, M is —P(═O)(OH)O⁻[CaOH]⁺ or —C(Y){P(═O)(OH)O⁻[CaOH]⁺}₂. Moretypically, M is —P(═O)(OH)O⁻[CaOH]⁺.

Phosphonic acid, sulfonic acid or carboxylic acid groups can beconverted into the corresponding salt forms using well-known methods,for instance by treatment with the appropriate base. For example,phosphonic acid groups, sulfonic acid groups or carboxylic acid groupscan be converted into calcium salts of those groups by treatment withcalcium hydroxide. In one embodiment of the process of the invention forproducing a substrate having an adhesive surface, M is a group havingthe structure —P(═O)(OH)₂; —C(Y)[P(═O)(OH)₂]₂; —C(═O)OH; —CY(COOH)₂;—S(═O)₂OH or —CY[S(═O)₂OH]₂, wherein Y is H, C₁₋₆ alkyl, aryl, —OH, —SHor NH₂, and the process further comprises the step of converting saidgroup into a salt of said group. Typically, the salt is a calcium salt.More typically, M is —P(═O)(OH)₂ and the salt is —P(═O)(OH)O⁻[CaOH]⁺.

Alternatively, M may be a group comprising one or more sulfonamidegroups. Accordingly, W_(A) or W_(B) is typically a group which comprisesat least one sulfonamide group. Thus, W_(A) or W_(B) can be a groupwhich comprises a single sulfonamide group, or a group which comprises aplurality of sulfonamide groups, such as a bis-sulfonamide group or apolysulfonamide group. Suitable M groups include —(═O)₂NH₂ and—CY[S(═O)₂NH₂]₂, wherein Y is H, C₁₋₆ alkyl, aryl, —OH, —SH or NH₂.Typically, W_(A) or W_(B) is -L²-S(═O)₂NH₂, C₁₋₂₀ alkyl, C₃₋₂₀cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl, wherein said C₁₋₂₀alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl and heteroaryl areeach substituted by -L²-S(═O)₂NH₂, wherein said C₁₋₂₀ alkyl isoptionally interrupted by N(R″), O, S or arylene, and wherein L² is asingle bond, C₁₋₆ alkylene, arylene, -arylene-C₁₋₆ alkylene- or —C₁₋₆alkylene-arylene-, wherein each of said C₁₋₆ alkylene groups isoptionally interrupted by N(R″), O, S or arylene. Groups comprisingsulfonamide moieties may be used for metal adhesion, or for adhesionthrough an ion exchange reaction or an ionic cross linking reaction.

Alternatively, M is a group comprising one or more carboxyl amidegroups. Accordingly, W_(A) or W_(B) is typically a group which comprisesat least one carboxyl amide group. Thus, W_(A) or W_(B) can be a groupwhich comprises a single carboxyl amide group, or a group whichcomprises a plurality of carboxyl amide groups, such as a bis-carboxylamide group or a poly(carboxyl amide) group. Suitable M groups include—C(═O)NH₂ and —CY[C(═O)NH₂]₂, wherein Y is H, C₁₋₆ alkyl, aryl, —OH, —SHor NH₂. Typically, W_(A) or W_(B) is -L²-C(═C)NH₂, C₁₋₂₀ alkyl, C₃₋₂₀cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl, wherein said C₁₋₂₀alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl and heteroaryl areeach substituted by -L²-C(═O)NH₂, wherein said C₁₋₂₀ alkyl is optionallyinterrupted by N(R″), O, S or arylene, and wherein L² is a single bond,C₁₋₆ alkylene, arylene, -arylene-C₁₋₆ alkylene- or —C₁₋₆alkylene-arylene-, wherein each of said C₁₋₆ allylene groups isoptionally interrupted by N(R″), O, S or arylene. Groups comprisingcarboxyl amide moieties may be used for metal adhesion, or for adhesionthrough an ion exchange reaction or an ionic cross linking reaction.

In the carbene precursor compounds of formula (I), used in the processfor producing a substrate having an adhesive surface, W_(A) or, wherepresent, W_(B), may comprise a group which is a precursor of an adhesivefunctional group.

The term “group which is a precursor of an adhesive functional group”,as used herein, refers to a group which may be converted into anadhesive functional group. Thus, a group which is a precursor of anadhesive functional group may be a protected version of the adhesivefunctional group, wherein deprotection of that group yields thecorresponding adhesive functional group. Alternatively (oradditionally), a group which is a precursor of an adhesive functionalgroup may one which can be converted into an adhesive functional groupin a single synthetic step.

Typically, W_(A) or, where present, W_(B), comprises a group which is aprecursor of an adhesive functional group when it is necessary toprotect the adhesive functional group during step (b) of the process ofthe invention for producing a substrate having an adhesive surface (i.e.during the step in which the carbene reactive intermediate is generatedfor reaction with the substrate). Then, once the reaction between thecarbene reactive intermediate and the substrate is complete, the groupwhich is a precursor of an adhesive functional group may be convertedinto the corresponding adhesive functional group.

Alternatively, the group which is a precursor of an adhesive functionalgroup may be converted into the corresponding adhesive functional groupduring step (b) of the process. Thus, in one embodiment of the processof the invention for producing a substrate having an adhesive surface,either W_(A) or W_(B) comprises a group which is a precursor of anadhesive functional group, and step (b), of generating a carbenereactive intermediate from the carbene precursor so that it reacts withthe substrate to functionalise the surface, is combined with step (c),of converting said group which is a precursor into an adhesivefunctional group.

A group which is a precursor of an adhesive functional group which maybe employed in the present invention is a group having the followingstructure:

wherein X¹ is a single bond, C(R″)(R′″), N(R″) or O, wherein R″ and R′″are independently selected from H, C₁₋₆ alkyl or aryl, and Prot is aprotecting group which is a precursor to a —CH═CH₂ group. Accordingly,W_(A) or W_(B) is typically a group which comprises at least one grouphaving the structure:

wherein X¹ and Prot are as defined above. Thus, W_(A) or W_(B) can be asingle group having that structure —X¹—C(═O)-Prot or a group whichcontains a plurality groups having the structure —X¹—C(═O)-Prot.Typically, W_(A) or W_(B) is

C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl,wherein said C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl andheteroaryl are each substituted by

wherein said C₁₋₂₀ alkyl is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl, and wherein L² is a singlebond, C₁₋₆ alkylene, arylene, -arylene-C₁₋₆ alkylene- or —C₁₋₆alkylene-arylene-, wherein each of said C₁₋₆ alkylene groups isoptionally interrupted by N(R″), O, S or arylene.

Such groups comprising

can be converted into an adhesive functional group having the followingstructure:

in which X¹ is as defined above. Thus, typically, in the process of theinvention for producing a substrate having an adhesive surface, eitherW_(A) or W_(B) comprises a group having the structure:

wherein X¹ and Prot are as defined above, and step (c) of the processcomprises converting said group into an adhesive functional group havingthe structure:

in which X¹ is as defined above. Typically, the conversion is effectedby electromagnetic irradiation, ultrasonic irradiation or thermalirradiation. More typically, the conversion is effected by thermalirradiation, for instance by heating. Typically, steps (b) and (c) arecombined such that conversion into the adhesive functional group takesplace during step (b), in which the carbene reactive intermediate isgenerated for reaction with the substrate.

Other groups which may be employed as precursors of adhesive functionalgroups include —OH and —NH(R″), wherein R″ is selected from H, C₁₋₆alkyl or aryl. Such groups may be converted into a group of thefollowing structure:

in which X¹ is O or N(R″). Thus, in one embodiment of the process of thepresent invention for producing a substrate having an adhesive surface,either W_(A) or W_(B) comprises a group which is a precursor of anadhesive functional group, which group which is a precursor is selectedfrom —OH and —NH(R″), wherein R″ is selected from H, C₁₋₆ alkyl or aryl,wherein step (c) of the process comprises reacting said —OH or —NH(R″)with Hal-C(O)C(R¹)═CR²R³, wherein Hal is a suitable leaving group andR¹, R² and R³, which may be the same or different, are each selectedfrom H, C₁₋₆ alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio andarylthio,

thereby converting said —OH or —NH(R″) into an adhesive functional grouphaving the following structure:

in which X¹ is O or N(R″). Typically, R¹ is H or cyano. Typically, R²and R³ are each H. Typically, Hal is a halo group, for instance Cl, Bror I. Alternatively, Hal may be any other suitable leaving group which,for reacting said —OH or —NH(R″) with Hal-C(O)C(R¹)═CR²R³, isfunctionally equivalent to a halo group such as Cl, Br or I.

Other groups which may be employed as precursors of adhesive functionalgroups include groups comprising an aliphatic carbon-carbon double bond.The aliphatic carbon-carbon double bond(s) of such groups can (each) beconverted into an epoxide adhesive functional group. Thus, in oneembodiment of the process of the present invention for producing asubstrate having an adhesive surface, either W_(A) or W_(B) comprises agroup which is a precursor of an adhesive functional group, which groupwhich is a precursor contains an aliphatic carbon-carbon double bond,wherein step (c) of the process comprises oxidising said aliphaticcarbon-carbon double bond to form an epoxide group, thereby convertingsaid group which is a precursor into an epoxide adhesive functionalgroup. Typically, the group which is a precursor of an adhesivefunctional group is of the following structure:

in which R¹, R² and R³, which may be the same or different, are eachselected from H, C₁₋₆ alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio andarylthio; and said epoxide adhesive functional group is of the followingstructure:

Typically, R¹, R² and R³ are independently selected from H, C₁₋₆ alkyland aryl. More typically, R¹, R² and R³ are each H.

Other groups which may be employed as precursors of adhesive functionalgroups include groups (denoted herein “M”) which are precursors ofgroups that are capable of adhering to a metal, a metal alloy or a metalion or salt. Thus, typically, either W_(A) or W_(B) of the carbeneprecursor compounds of the invention comprises a group which is aprecursor of a group that is capable of adhering to a metal, metalalloy, or a metal salt or ion. Accordingly, W_(A) or Ws is typically agroup which comprises at least one group, denoted “M”, that is aprecursor of a group that is capable of adhering to a metal, a metalalloy or a metal ion or salt. Thus, W_(A) or W_(B) can be a group whichcomprises a single “M” group or a group which comprises a plurality of“M” groups. Typically, W_(A) or W_(B) is -L²-M, C₁₋₂₀ alkyl, C₃₋₂₀cycloalkyl, C₃₋₂₀ heterocyclyl, aryl or heteroaryl, wherein said C₁₋₂₀alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl and heteroaryl areeach substituted by -L²-M, wherein said C₁₋₂₀ alkyl is optionallyinterrupted by N(R″), O, S or arylene, wherein R″ is H, C₁₋₆ alkyl oraryl, and wherein L² is a single bond, C₁₋₆ alkylene, arylene,-arylene-C₁₋₆ alkylene- or —C₁₋₆ alkylene-arylene-, and wherein each ofsaid C₁₋₆ alkylene groups is optionally interrupted by N(R″), O, S orarylene.

Typically, said group M which is a precursor of a group that is capableof adhering to a metal, a metal alloy or a metal salt is eitherP(═O)(OR⁴)₂ or:

wherein R⁴ is C₁₋₆ alkyl or aryl; and Y is H, C₁₋₆ alkyl, aryl, —OH, —SHor NH₂. Those groups may be converted into the corresponding phosphonicacid groups. If required, the resulting phosphonic acid groups can beconverted into salts (for instance, calcium salts) of those phosphonicacid groups.

In one embodiment of the process of the present invention for producinga substrate having an adhesive surface, either W_(A) or W_(B) comprisesa group which is a precursor of a group that is capable of adhering to ametal, a metal alloy or a metal salt, wherein step (c) of the processcomprises converting said group which is a precursor into a group thatis capable of adhering to a metal, a metal alloy or a metal salt.Typically, said group which is a precursor of a group that is capable ofadhering to a metal, a metal alloy or a metal salt is either P(═O)(OR⁴)₂or:

and step (c) of the process comprises converting said group which is aprecursor into the corresponding phosphonic acid group having thestructure —P(═O)(OH)₂ or:

wherein R⁴ is C₁₋₆ alkyl or aryl; and Y is H, C₁₋₆ alkyl, aryl, —OH, —SHor NH₂. The process may further comprise the step of: (d) convertingsaid phosphonic acid group having the structure —P(═O)(OH)₂ or:

wherein R⁴ is C₁₋₆ alkyl or aryl and Y is H, C₁₋₆ alkyl, aryl, —OH, —SHor NH₂, into a salt of said phosphonic acid group. Typically, said saltis a calcium salt. More typically, the phosphonic acid group has thestructure —P(═O)(OH)₂ and the salt has the structure—P(═O)(OH)O⁻[CaOH]⁺.

Typically, in the compounds of the invention of formula (I), W_(A) andW_(B) are independently selected from:

-L²-OH, -L²-NH₂, -L²-M, C₁₋₂₀ alkyl, C₃₋₂₀-cycloalkyl, C₃₋₂₀heterocyclyl, aryl and heteroaryl,

wherein said C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl andheteroaryl are each substituted by one or more groups selected from:

-L²-OH, -L²-NH₂, -L²-SH and -L²-M, and wherein said C₁₋₂₀ alkyl isoptionally interrupted by N(R″), O, S or arylene, wherein R″ is asdefined in claim 1;

X¹ is a single bond, C(R″)(R′″), N(R″) or O, wherein R″ is as defined inclaim 1 and R′″ is H, C₁₋₆ alkyl or aryl;

Prot is a protecting group which is a precursor to a —CH═CH₂ group;

L² is a single bond, C₁₋₆ alkylene, arylene, -arylene-C₁₋₆ alkylene- or—C₁₋₆ alkylene-arylene-, wherein each of said C₁₋₆ alkylene groups isoptionally interrupted by N(R″), O, S or arylene, wherein R″ is asdefined in claim 1, provided that when L² is a single bond the

groups

-L²-OH, -L²-NH₂ and -L²-SH may not be bonded directly to X;

R¹, R² and R³, which may be the same or different, are each selectedfrom H, alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio andarylthio; and

M is selected from a group that is capable of adhering to a metal, ametal alloy, or a metal salt, and a group which is a precursor of agroup that is capable of adhering to a metal, metal alloy or a metalsalt. Such compounds may be used in the process of the invention forproducing a substrate having an adhesive surface, provided that whereW_(A) or W_(B) comprises the group:

step (c) of the process comprises converting said group into one of thefollowing structure:

and

provided that where W_(A) or W_(B) comprises a group which is aprecursor of a group that is capable of adhering to a metal, metal alloyor a metal salt, step (c) of the process comprises converting said groupwhich is a precursor into a group that is capable of adhering to ametal, a metal alloy or a metal salt. Typically, R¹ is H or cyano.Typically, R² and R³ are independently selected from H, C₁₋₆ alkyl andaryl. More typically, R² and R³ are each H.

The substrates of the invention having a functionalised surface arefunctionalised with one or more groups of the following formula (II):

wherein R, *, A, L_(A), W_(A) and y are as defined above.

In the substrates of the invention having a functionalised surface, thegroups W_(A) and W_(B) comprise one or more adhesive functional groupsor one or more groups which are precursors of adhesive functionalgroups. Where W_(A) or W_(B) comprises a group which is a precursor ofadhesive functional group, it is understood that the substrate may betreated in order to convert that group into the corresponding adhesivefunctional group. In one embodiment of the substrate of the inventionhaving a functionalised surface, M is selected from: —P(═O)(OR⁴)₂;—P(═O)(OH)₂ or a salt thereof;

or a salt thereof; —C(═O)OH or a salt thereof; —CY(COOH)₂ or a saltthereof; —S(═O)₂OH or a salt thereof; —CY[S(═O)₂OH]₂ or a salt thereof;—C(═O)NH₂; —CY[C(═O)NH₂]2; —S(═O)₂NH₂; and —CY[S(═O)₂NH₂]2 wherein R⁴ isC₁₋₆ alkyl or aryl; and Y is H, C₁₋₆ alkyl, aryl, —OH, —SH or NH₂. Inone embodiment, M is a calcium salt of a group having any one of thefollowing structures: —P(═O)(OH)₂, -C(═O)OH, —CY(COOH)₂, —S(═O)₂OH,—CY[S(═O)₂OH]₂ and:

Typically, the calcium salt is —P(═O)(OH)O⁻[CaOH]⁺.

Typically, said group containing an aliphatic carbon-carbon double bondof the substrate of the invention having a functionalised surface isselected from:

wherein R¹, R² and R³, which may be the same or different, are eachselected from H, C₁₋₆ alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio andarylthio; and X¹ is a single bond, O, N(R″) or C(R″)(R″′), wherein R″and R′″ are independently selected from H, C₁₋₆ alkyl and aryl.

Typically, said group containing an epoxide group of the substrate ofthe invention having a functionalised surface has the followingstructure:

in which R¹, R² and R³, which may be the same or different, are eachselected from H, C₁₋₆ alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio andarylthio.

More typically, W_(A) and W_(B) of the substrate of the invention havinga functionalised surface are independently selected from:

-L²-NH₂, -L²-SH, -L²-M, C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀heterocyclyl, aryl and heteroaryl,

wherein said C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ heterocyclyl, aryl andheteroaryl are each substituted by one or more groups selected from:

-L²-OH, -L²-NH₂, -L²-SH and -L²-M, and wherein said C₁₋₂₀ alkyl isoptionally interrupted by N(R″), O, S or arylene, wherein R″ is asdefined above;

X¹ is a single bond, C(R″)(R′″), N(R″) or O, wherein R″ and R′″ are asdefined above;

Prot is a protecting group which is a precursor to a —CH═CH₂ group;

L² is a single bond, C₁₋₆ alkylene, arylene, -arylene-C₁₋₆ alkylene- or—C₁₋₆ alkylene-arylene-, wherein each of said C₁₋₆ alkylene groups isoptionally interrupted by N(R″), O, S or arylene wherein R″ is asdefined in claim 1;

R¹, R² and R³, which may be the same or different, are each selectedfrom H, C₁₋₆ alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio andarylthio; and

M is as defined hereinbefore. Typically, R¹ is H or cyano. Typically, R²and R³ are independently selected from H, C₁₋₆ alkyl and aryl. Moretypically, R² and R³ are each H.

The carbene precursor compounds of formula (I) used in the process ofthe invention for producing a substrate having an adhesive surface aretypically other than each of the following compounds:

1-{2-[4-(diazo-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)phenyl phenyl diazomethane,bis-4,4′-N,N-dimethylamino diphenyldiazomethane,4-([3,4-dimethoxyphenyl]oxymethyl)phenyl phenyl diazomethane and4-([3-N,N-diethylaminophenyl]oxymethyl)phenyl phenyl diazomethane.

In the carbene precursor compound of formula (I) used in the process ofthe invention for producing a substrate having an adhesive surface, thecorresponding substrates of the invention, and the substrates of theinvention which are functionalised with a group of formula (II),-L_(A)-W_(A) and, where present, -L_(A)-W_(B), are typically other than—NMe₂.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other than—N═N—Ar^(P), wherein Ar^(P) is an unsubstituted or substituted phenylgroup. Typically, Ar^(P) is:

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other than—CH₂OR^(QQ) wherein R^(QQ) is N-ethyl-N-phenyl-2-aminoethyl,3,4-dimethoxyphenyl or 3-N,N-dimethylaminophenyl.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other than—N⁺Me₂O⁻.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other than—CH₂O(CH₂)₂N(H)C(O)N(H)Ph.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other than—CH₂O(CH₂)₂N(Ph)CH₂CH₃.

More typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are otherthan each of the following moieties:

—CH₂OR^(QQ) wherein R^(QQ) is N-ethyl-N-phenyl-2-aminoethyl,3,4-dimethoxyphenyl or 3-N,N-dimethylaminophenyl;

—NMe₂;

—N⁺Me₂O⁻;

—CH₂O(CH₂)₂N(H)C(O)N(H)Ph;

—CH₂O(CH₂)₂N(Ph)CH₂CH₃; and

—N═N—Ar^(P), wherein Ar^(P) is an unsubstituted or substituted phenylgroup.

Typically, Ar^(P) is:

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other thanhydrogen.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other thanhydrogen and other than Q^(P), wherein:

Q^(P) is selected from N(Z₁ ^(P))(Z₂ ^(P)) andCH₂—V^(P)—(W^(P)—R^(P))_(a);

Z₁ ^(P) and Z₂ ^(P) are independently selected from aryl which isunsubstituted or substituted, heteroaryl which is unsubstituted orsubstituted, C₁₋₁₀ alkoxy which is unsubstituted or substituted, C₁₋₁₀alkylamino which is unsubstituted or substituted, di(C₁₋₁₀)alkylaminowhich is unsubstituted or substituted, C₁₋₁₀ alkylthio which isunsubstituted or substituted, and C₁₋₁₀ alkyl which is unsubstituted orsubstituted and which is optionally interrupted by N(R^(2P)), O or Swherein R^(2P) is H or C₁₋₆ alkyl;

V^(P) is C₁₋₁₀ alkylene, —O—C₁₋₁₀ alkylene-, —C₁₋₁₀ alkylene-O— or—O-C₁₋₁₀ alkylene-O—;

W^(P) is a functional group of one of the following formulae (a) to (c):

wherein X^(P) is O, S or NH₂ ⁺;

R^(P) is selected from H, C₁₋₆ alkyl which is unsubstituted orsubstituted, aryl which is unsubstituted or substituted and heteroarylwhich is unsubstituted or substituted; and

a is 1, 2 or 3.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other thanhydrogen and other than —CH₂OR^(Q), wherein:

R^(Q) is Ar^(1Q) or (CH₂)_(b)N(R¹NR^(2Q));

Ar^(1Q) is:

wherein Y^(Q) is C₁₋₄ alkoxy or N(R^(3Q))(R^(4Q));

R^(3Q) and R^(4Q), which may be the same or different, are C₁₋₄ alkyl;

c is 0 or an integer of 1 to 3;

R^(1Q) is C₁₋₄ alkyl;

R^(2Q) is phenyl; and

b is an integer of 1 to 4.

More typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are otherthan hydrogen and other than Q^(P) and other than —CH₂OR^(Q), whereinQ^(P) and R^(Q) are as defined above.

Further typical features of the carbene precursor compounds of formula(I), the corresponding substrates of the invention, and the substratesof the invention which are functionalised with a group of formula (II),are set out as follows:

Typically, A is aryl. More typically, A is phenyl.

Typically, R is selected from unsubstituted or substituted aryl,unsubstituted or substituted heteroaryl, H, CF₃ and tert-butyl. Moretypically, R is selected from unsubstituted or substituted phenyl, H,CF₃ and tert-butyl. More typically, R is unsubstituted or substitutedphenyl.

The reactivity of the diazo compound and its derived carbene can bemodified by including electron releasing or electron withdrawing groupson the aromatic rings. In addition, the solubility of the diazo compoundand its derived carbene can be modified by including groups of a givenhydrophilicity or lipophilicity on the aromatic rings. Thus, suitablesubstituents for A or R (wherein R is substituted aryl, e.g. substitutedphenyl, or substituted heteroaryl) include C₁₋₆ alkyl, aryl, cyano,amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonicacid, and sulfonyl. More typically, substituents for A or R (wherein Ris substituted aryl, e.g. substituted phenyl, or substituted heteroaryl)are selected from methyl, ethyl, propyl, butyl, —CN, —NH₂, keto,—C(═O)NH₂, —OH, halo, —COOH, —COOMe and —SH.

The or each group -L_(A)-W_(A) and the or each group -L_(B)-W_(B) mayoccupy any available position on the aryl or heteroaryl ring to whichthe group is bonded. Thus, when parameter “y” is 1, A ismono-substituted at any ring position by -L_(A)-W_(A); for instance,when A is a phenyl group it may be substituted at any of positions 2, 3,4, 5 and 6. When parameter “y” is 2, A is di-substituted at any twopositions by -L_(A)-W_(A); for instance, when A is a phenyl group it maybe 2,3-2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted. When parameter “y”is 3, A is tri-substituted at any three positions by -L_(A)-W_(A); forinstance, when A is a phenyl group it may be 2,3,4-, 2,4,5- or3,4,5-tri-substituted. Likewise, when R is aryl or heteroaryl, said arylor heteroaryl may be mono-substituted at any ring position by-L_(B)-W_(B). In that case, when R is a phenyl group it may besubstituted at any of positions 2, 3, 4, 5 and 6. Alternatively, saidaryl or heteroaryl R may be di-substituted at any ring position by-L_(B)-W_(B). In that case, when R is a phenyl group, it may be2,3-2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted. Alternatively, saidaryl or heteroaryl R may be tri-substituted at any ring position by-L_(B)-W_(B). In that case, when R is a phenyl group, it may be 2,3,4-,2,4,5- or 3,4,5-tri-substituted.

Typically, y is 1.

Typically, when R is aryl or heteroaryl, said aryl or heteroaryl is notsubstituted by -L_(B)-W_(B). However, when said aryl or heteroaryl issubstituted by -L_(B)-W_(B), said aryl or heteroaryl R is typicallymono-substituted by -L_(B)-W_(B).

Typically, L_(A) is a single bond or C₁₋₂₀ alkylene which is substitutedor unsubstituted and optionally interrupted by N(R″), O, S or arylene,wherein R″ is H, C₁₋₆ alkyl or aryl. More typically, L_(A) is a singlebond or C₁₋₆ alkylene which is optionally interrupted by O. For example,L_(A) may be a single bond, methylene, ethylene, propylene, butylene,pentylene or hexylene, wherein said ethylene, propylene, butylene,pentylene or hexylene, are either uninterrupted or interrupted by asingle oxygen atom. L_(A) may be methylene or —CH₂—O—CH₂—.

Typically, L₂, as used herein, is a single bond or a C₁₋₆ alkylene whichis substituted or unsubstituted and optionally interrupted by N(R″), O,S or arylene, wherein R″ is H, C₁₋₆ alkyl or aryl. More typically, L₂ isa single bond or unsubstituted C₁₋₆ alkylene which is uninterrupted orinterrupted by a single oxygen atom. Even more typically, L₂ is a singlebond, methylene, ethylene, propylene, butylene, pentylene or hexylene.

Typically R″, as used herein, is H, methyl, ethyl or phenyl. Moretypically, R″ is H.

Typically R′″, as used herein, is H, methyl, ethyl or phenyl. Moretypically, R′″ is H.

Typically, the carbene precursor compound of formula (I) is selectedfrom:

-   [4-(Diazo(phenyl)methyl)phenyl]methanol;-   7-Oxa-bicyclo[2.2.1]hept-5-ene-2-carboxylic    acid-4-(diazo-phenylmethyl)-benzyl ester;-   1-(allyloxymethyl)-4-(diazo(phenyl)methyl)benzene; and-   [4-(Diazo-phenyl-methyl)-benzyl]phosphonic acid diethyl ester.

Thus, typically, the process of the invention for producing a substratehaving a functionalised surface comprises:

(a) contacting the substrate with a carbene precursor, which carbeneprecursor is selected from:

-   [4-(Diazo(phenyl)methyl)phenyl]methanol;-   7-Oxa-bicyclo[2.2.1]hept-5-ene-2-carboxylic    acid-4-(diazo-phenylmethyl)-benzyl ester;-   1-(allyloxymethyl)-4-(diazo(phenyl)methyl)benzene; and-   [4-(Diazo-phenyl-methyl)-benzyl]phosphonic acid diethyl ester; and

(b) generating a carbene reactive intermediate from the carbeneprecursor so that it reacts with the substrate to functionalise thesurface, thereby yielding said substrate having a functionalisedsurface.

The process of the invention for producing a substrate having anadhesive surface may comprise reacting the substrate with a plurality ofdifferent carbene precursors, typically simultaneously. Simultaneousreaction with two or more different carbene precursors typically resultsin the production of a substrate whose surface is functionalised with arandom mixture of the different carbene functionalities.

Accordingly, in one embodiment, the process of the invention forproducing a substrate having an adhesive surface further comprises:

(a′) contacting the substrate with a further carbene precursor, whichfurther carbene precursor is a compound of formula (I) as definedherein, which compound is different from the carbene precursor used instep (a); and

(b′) generating a carbene reactive intermediate from the further carbeneprecursor so that it reacts with the substrate to functionalise thesurface.

Typically, step (b′) comprises either:

(i′) when W_(A) or W_(B) of said further carbene precursor comprises anadhesive functional group, generating a carbene reactive intermediatefrom the further carbene precursor so that it reacts with the substrateto functionalise the surface; or

(ii′) when W_(A) or W_(B) in said further carbene precursor comprises aprecursor of a adhesive functional group, generating a carbene reactiveintermediate from the further carbene precursor so that it reacts withthe substrate to functionalise the surface, and (c′) converting saidgroup which is a precursor into an adhesive functional group.

Typically, steps (a) and (a′) occur simultaneously. Typically, thegenerations of the carbene reactive intermediates in steps (b) and (b′)occur simultaneously.

The substrate treated in accordance with the present invention may beany natural or synthetic substrate which is capable of reaction with acarbene reactive intermediate generated from a diarylcarbene precursorof formula (I) as defined above.

Typically the substrate is, or comprises, a natural or synthetic polymerincluding but not limited to cellulose, polyglycoside, polypeptides,polyacrylates, polyacrylics, polyamides, polyimides, polycarbonates,polyesters, epoxy resins, polyethers, polyketones, polyolefins, rubbers,polystyrenics, polysulfones, polyurethanes, polyvinyls and theirco-polymers.

Where the substrate comprises a polymer, the molecular weight of thepolymeric substrate may be selected according to the particular utilityof the end product.

In one embodiment, the substrate is selected from polyesters,polyacrylates, polyolefins, polyamides, polyimides, polysulfones andepoxy resins. Typically the polyolefin is a homopolymer or copolymer ofethylene, propylene, styrene, PET (polyethylene terephthalate) or EPDM(ethylene propylene diene monomer).

The polymer may be a homopolymer or a copolymer, for instance a blockcopolymer. It may thus be derived from monomeric units which are thesame or different.

The polymer may be modified, for instance by admixture with anotherorganic or inorganic material. The substrate may thus comprise both apolymer and an inorganic material, for instance a mixture of a polymerand an inorganic material such as an inorganic filler. The substratemay, for example, comprise a mixture of one or more of the polymersreferred to above and one or more of the inorganic materials referred toherein. Modified polymers of this type are suitable for use in, forinstance, semiconductor applications. Technical problems can arise whenpolymers are used as coating or bonding agents with semiconductors, forexample owing to their different behaviour on heating. The inclusion ofan inorganic filler with a polymer serves to modify the thermalproperties of the polymer and make it better suited for use togetherwith a semiconductor.

In one embodiment, the substrate is, or comprises, a thermoplastic resinor a thermosetting resin.

The substrate may be, or comprise, an inorganic material including butnot limited to a metal, a metal alloy, or a metal salt, silica, glasses,alumina, titania, and allotropes of carbon such as diamond, diamond-likecarbon, graphite, fullerenes and nanotubes.

In one embodiment the substrate is a metal or an alloy of a metal, whichmetal is any metal other than an alkali metal or an alkaline earthmetal. Typically, the metal other than an alkali metal or an alkalineearth metal or alloy is selected from: Al, Cu, Pb, Au, Ag, Pt, Pd andSn. The metal may also include group IV (group 14) elements, for exampleGe and Si. The metallisation of polymer surfaces is of relevance inprinted circuit board and electronic technology. Thus, adhesion of suchmetals or alloys to other materials may be of use in the electronicsindustry, for example in the manufacture of printed circuit boards.Alternatively, the substrate is a salt of a metal. Typically, the metalsalt is a calcium salt.

Typically, the substrate is, or comprises, a nanoparticle or amicroparticle. More typically, the substrate is, or comprises, a highmolecular weight material which is a nanoparticle or a microparticle.

As used herein, the term “microparticle” means a microscopic particlewhose size is measured in micrometres (μm). Typically, the microparticlehas an average diameter of from 1 μm to 1000 μm. More typically, themicroparticle has an average diameter of from 1 μm to 500 μm, forinstance from 1 μm to 250 μm. Most typically, the microparticle has anaverage diameter of from 1 μm to 100 μm.

As used herein, the term “nanoparticle” means a microscopic particlewhose size is measured in nanometres (nm). Typically, the nanoparticlehas an average diameter of from 1 nm to 1000 nm. More typically, thenanoparticle has an average diameter of from 5 nm to 500 μm, forinstance from 5 μm to 250 μm. Most typically, the nanoparticle has anaverage diameter of from 5 μm to 100 μm. Thus, in one embodiment thesubstrate is, or comprises, C₆₀. In another embodiment the substrate is,or comprises, a nanotube. Typically, the nanotube is a carbon nanotube.The nanotube may however comprise atoms other than carbon.

In one embodiment the substrate is, or comprises, a pigment. The pigmentmay be any colouring agent made from a natural or synthetic substance.

Typically, the substrate is, or comprises, a nanoparticle or amicroparticle, which nanoparticle or microparticle is, or comprises, apigment.

In one embodiment, the substrate is, or comprises, textile.

In another embodiment, the substrate is, or comprises, paper.

The substrate may comprise any two or more of the above-listedmaterials.

The substrate treated in accordance with the present invention may be inany suitable physical form. Thus, the substrate may be in the form of afilm, a layer, a sheet or a board. Alternatively, the substrate may bein powder form, or in the form of pellets, beads, particles,nanoparticles or microparticles. The pellets, beads or particles may bemacroscopic particles, i.e. visible to the naked eye, or microscopicparticles. Thus, the particles could be microparticles or nanoparticles.

In step (a) of the process of the invention for producing a substratehaving an adhesive surface, the substrate is contacted with the carbeneprecursor, which is a compound of formula (I). Typically, the substrateis contacted with the carbene precursor by dip coating, spray coating,rolling, printing or co-extrusion. The dip coating, spray coating,rolling, printing or co-extrusion may be performed in solution orotherwise. Thus, the dip coating, spray coating, rolling, printing orco-extrusion may be performed using a solution of the carbene precursoror using the neat carbene precursor. Similarly, the dip coating, spraycoating, rolling, printing or co-extrusion may be carried out using theneat substrate or using a suitable solution of the substrate.

Typically, the neat substrate is dipped in or sprayed with the neatcarbene precursor or a solution of the carbene precursor, in order toform a coating on a surface of the substrate, which coating comprisesthe carbene precursor. Alternatively, the neat carbene precursor or asolution thereof may be applied to the substrate by printing it, or byrolling it, onto the surface of the substrate. In another embodiment,the substrate and carbene precursor are contacted by co-extruding thesubstrate and carbene precursor.

In step (b) of the process of the present invention for producing asubstrate having an adhesive surface, the generated carbene intermediatereacts with the substrate to functionalise the surface. In this context,the term “surface” means either the whole of the surface of thesubstrate or only a portion of the surface of the substrate.

The carbene reactive intermediate is typically generated by a thermalprocess and/or by an irradiation process. Typically, the carbenereactive intermediate is generated by thermal irradiation, for instanceby heating. This heat might be applied externally, but may also be as aresult of another process, for example, extrusion. Alternatively, thecarbene reactive intermediate may be generated by electromagneticradiation, for instance by UV, microwave or laser irradiation, or byultrasonic irradiation. Some of these techniques, including laser and UVirradiation, are suitable for generation of the carbene reactiveintermediate selectively, i.e. on only a portion of the surface of thesubstrate.

Typically, only a portion of the surface of the substrate isfunctionalised. For example, the surface may be modified in certainareas only, to form specific a “pattern” of surface functionalisation.In this way, the two-dimensional-shape-of-the-resulting adhesive surfacemay be controlled. This may be useful in the design of printed circuitboards, for example, where the adhesion of metal to substrate is onlydesired in certain specific places.

In one embodiment, the carbene reactive intermediate is generatedselectively, i.e. only on certain portions of the surface of thesubstrate. In this way, only the particular regions of the surface onwhich the carbene reactive intermediate has been generated becomefunctionalised. This is known as “selective activation”, and can be usedto form specific a “pattern” of surface functionalisation.

Accordingly, in one embodiment of the process of the invention forproducing a substrate having an adhesive surface, the generation of saidcarbene reactive intermediate in step (b) is performed on only a portionof the surface of the substrate.

Such selective activation can be achieved using “directed activation”,which may involve irradiation of certain portions of the surface only.Such directed activation can be achieved, for instance, by laser writingor by UV writing.

Alternatively, such selective activation can be achieved by masking aportion of the surface of the substrate, followed by activation (i.e.generation of the carbene reactive intermediate) on only the unmaskedparts of the surface. Usually, this is followed by removal of the maskand washing of the surface to remove unreacted material.

The selective activation process may be repeated any number of times,leading to the build-up of a complex pattern of surfacefunctionalisation in a controlled way.

Alternatively, in order that only a portion of the surface of asubstrate is functionalised, the surface may be masked before contactingthe substrate with the carbene precursor in step (a). Again, in this waythe carbene reactive intermediate only contacts, and subsequently onlyreacts with, the unmasked areas of the substrate, and does not reactwith the masked areas.

Additionally or alternatively, chemical patterning techniques, such asselective irradiation, ink jet printing or screen printing (where thecarbene precursor compound is used as the printing medium) can be usedto control exactly which parts of the surface of the substrate areexposed to the carbene precursor compound (and consequently the carbenereactive intermediate), and consequently, which parts of the surface arefunctionalised.

For example, by ink jet printing a solution of the carbene precursorcompound onto the surface of the substrate in certain places only, thesurface may be functionalised with the carbene reactive intermediate incertain places only. The resulting adhesive surface will then have aspecific two-dimensional pattern, such that an adherend adheres ontothat pattern only.

Such chemical patterning techniques and selective activation techniquescan be performed more than once and/or in combination with one another,leading to the build-up of a complex pattern of surface modification.

In one embodiment of the process of the invention for producing asubstrate having an adhesive surface, step (a) comprises contacting thesubstrate with said carbene precursor using chemical patterning.Additionally or alternatively, the process of the invention forproducing a substrate having an adhesive surface further comprisesmasking the substrate prior to contacting said substrate with saidcarbene precursor.

In one embodiment of the process of the invention for producing asubstrate having an adhesive surface, the process further comprises thestep of contacting the adhesive surface of said substrate, or a partthereof, with an adherend, under conditions which cause adhesion of saidsubstrate to said adherend.

Typically, the adherend comprises a polymer, an inorganic material, abiological cell or biological tissue.

When the adherend comprises a polymer, the polymer is typically anatural or synthetic polymer including but not limited to cellulose,polyglycoside, polypeptides, polyacrylates, polyacrylics, polyamides,polyimides, polycarbonates, polyesters, epoxy resins, polyethers,polyketones, polyolefins, rubbers, polystyrenics, polysulfones,polyurethanes, polyvinyls and their co-polymers. In one embodiment, theadherend is selected from polyesters, polyacrylates, polyolefins,polyamides, polysulfones and epoxy resins. Typically the adherend is ahomopolymer or copolymer of ethylene, propylene, styrene, PET(polyethylene terephthalate) or EPDM (ethylene propylene diene monomer).The polymer may be a homopolymer or a copolymer, for instance a blockcopolymer. It may thus be derived from monomeric units which are thesame or different. The polymer may be modified, for instance byadmixture with another organic or inorganic material. The adherend maythus comprise both a polymer and an inorganic material, for instance amixture of a polymer and an inorganic material such as an inorganicfiller. The adherend may, for example, comprise a mixture of one or moreof the polymers referred to above and one or more of the inorganicmaterials referred to above.

In one embodiment, the adherend is, or comprises, a thermoplastic resinor a thermosetting resin.

The adherend may be, or comprise, an inorganic material including butnot limited to a metal, a metal alloy, or a metal salt, silica, glasses,alumina, titania, and allotropes of carbon such as diamond, diamond-likecarbon, graphite, fullerenes and nanotubes.

In one embodiment the adherend is a metal or an alloy of a metal, whichmetal is any metal other than an alkali metal or an alkaline earthmetal. Typically, the metal other than an alkali metal or an alkalineearth metal or alloy is selected from: Al, Cu, Pb, Au, Ag, Pt, Pd andSn. The metal may also include group IV (group 14) elements, for exampleGe and Si. The metallisation of polymer surfaces is of relevance inprinted circuit board and electronic technology. Thus, adhesion of suchmetals or alloys to substrate materials may be of use in the electronicsindustry, for example in the manufacture of printed circuit boards.

Typically, the adherend is, or comprises, a nanoparticle or amicroparticle. More typically, the adherend is, or comprises, a highmolecular weight material which is a nanoparticle or a microparticle.

Thus, in one embodiment the adherend is, or comprises, C₆₀. In anotherembodiment the adherend is, or comprises, a nanotube. Typically, thenanotube is a carbon nanotube. The nanotube may, however, comprise atomsother than carbon.

In one embodiment the adherend is, or comprises, a pigment. The pigmentmay be any colouring agent made from a natural or synthetic substance.

Typically, the adherend is, or comprises, a nanoparticle or amicroparticle, which nanoparticle or microparticle is, or comprises, apigment.

In one embodiment, the adherend is, or comprises, textile.

In another embodiment, the adherend is, or comprises, paper.

The adherend may comprise any two or more of the above-listed materials.

The adherend may be present in any suitable physical form. Thus, theadherend may be in the form of a film, a layer, a sheet or a board.Alternatively, the adherend may be in powder form, or in the form ofpellets, beads, particles, nanoparticles or microparticles. The pellets,beads or particles may be macroscopic particles, i.e. visible to thenaked eye, or microscopic particles. Thus, the particles could bemicroparticles or nanoparticles.

As mentioned above, certain types of adhesive functional groups arecapable of interaction with certain types of adherends. Thus, byselecting a suitable adhesive functional group, the substrate can beadhered to a particular adherend as desired (for example to any of theadherends referred to above). Generally, a suitable adhesive functionalgroup is one which is capable of physical interaction with the adherend(e.g. due to an electrostatic attraction between adhesive functionalgroup and adherend) or capable of forming a chemical bond with theadherend (e.g. a covalent bond, ionic bond, hydrogen bond or othernon-covalent bond). Typically, a suitable adhesive functional group isstructurally similar to one or more of the chemical moieties present inthe adherend itself. For example, epoxy or alcohol functional groupswould be suitable for adhering a substrate to an epoxy resin adherend,and acrylate or other α,β-unsaturated ketone groups, or amine functionalgroups would be suitable for adhering a substrate to a polyacrylateadherend.

Table 1 below lists various adherends, and, for each adherend, someexamples of suitable adhesive functional groups that would be expectedto aid adhesion to the adherend.

TABLE 1 Examples of suitable adhesive Adherend functional groups EpoxyResin

R—NH₂ R—OH R—SH Polyacrylate

R—NH₂ R—SH Polystyryl

Polyolefin R—OH R—NH₂ R—SH

Polyurethane R—OH R—NH₂ R—SH Metal, Metal salt, Biological cell,Biological tissue

and salts thereof, for example calcium salts R—OH R—NH₂ R—SH PolyesterR—OH R—NH₂ R—SH Polyamide R—OH R—NH₂ R—SH Polycarbonate R—OH R—NH₂ R—SHPolyimide R—OH R—NH₂ R—SH

By selecting a suitable adhesive functional group, the substrate can beadhered to a particular adherend as desired. Thus, the process of theinvention for producing a substrate having an adhesive surface may beused to achieve improved adhesion in polymer, paper, textile and othermaterial composites, hybrids and laminates.

The process may also be used for the modification of thermoplastic andthermosetting resins.

The invention further provides a carbene precursor compound of thefollowing formula (I):

wherein:

A is an aryl or heteroaryl ring;

y is 1, 2, 3, 4 or 5;

L_(A) is a single bond, -alk-, -arylene-, -alk-arylene-, -X-alk-,-X-alk-X-, -X-arylene-, X-arylene-X-, -X-alk-arylene-, -alk-X-arylene-,-alk-arylene-X, -X-alk-X-arylene-, -alk-X-arylene-X- or-X-alk-X-arylene-X-, wherein X is N(R″), O, or S and wherein alk isC₁₋₂₀ alkylene which is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl;

W_(A) is a group comprising an adhesive functional group or a groupwhich is a precursor of an adhesive functional group;

R is selected from hydrogen, aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above;

provided that when R is aryl or heteroaryl, said aryl or heteroaryl maybe unsubstituted or substituted by one, two, three, four or five groups,which groups are independently selected from C₁₋₆ alkyl, aryl, cyano,amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonicacid, sulfonyl and -L_(B)-W_(B), wherein L_(B) is as defined above forL_(A) and is the same as or different from L_(A), and W_(B) is asdefined above for W_(A) and is the same as or different from W_(A),

provided that the compound is not:4,4′-bis(N-acetyl-2-aminoethyl)diphenyldiazomethane,1-{2-[4-(diazo-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)phenyl phenyl diazomethane,bis-4,4′-N,N-dimethylamino diphenyldiazomethane,4-([3,4-dimethoxyphenyl]oxymethyl)phenyl phenyl diazomethane,4-([3-N,N-diethylaminophenyl]oxymethyl)phenyl phenyl diazomethane or4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)phenyl phenyl diazomethane.

Typically, R is selected from aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above, provided that R is not CF₃.

Typically, the compound of formula (I) is not4,4′-bis(N-acetyl-2-aminoethyl)diphenyldiazomethane,1-{2-[4-(diazo-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)phenyl phenyl diazomethane,bis-4,4′-N,N-dimethylamino diphenyldiazomethane,4-([3,4-dimethoxyphenyl]oxymethyl)phenyl phenyl diazomethane,4-([3-N,N-diethylaminophenyl]oxymethyl)phenyl phenyl diazomethane orbis-4,4′-tert-butyl ester diphenyldiazomethane.

The diazo carbene precursor compounds of formula (I) may be prepared byoxidising the corresponding hydrazone compound. Accordingly, the presentinvention provides a process for producing a carbene precursor compoundof formula (I):

wherein

A is an aryl or heteroaryl ring;

y is 1, 2, 3, 4 or 5;

L_(A) is a single bond, -alk-, -arylene-, -alk-arylene-, -X-alk-,-X-alk-X-, -X-arylene-, X-arylene-X-, -X-alk-arylene-, -alk-X-arylene-,-alk-arylene-X, -X-alk-X-arylene-, -alk-X-arylene-X- or-X-alk-X-arylene-X-, wherein X is N(R″), O, or S and wherein alk isC₁₋₇₀ alkylene which is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl;

W_(A) is a group comprising an adhesive functional group or a groupwhich is a precursor of an adhesive functional group;

R is selected from hydrogen, aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above;

provided that when R is aryl or heteroaryl, said aryl or heteroaryl maybe unsubstituted or substituted by one, two, three, four or five groups,which groups are independently selected from C₁₋₆ alkyl, aryl, cyano,amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonicacid, sulfonyl and -L_(B)-W_(B), wherein L_(B) is as defined above forL_(A) and is the same as or different from L_(A), and W_(B) is asdefined above for W_(A) and is the same as or different from W_(A),

provided that the compound is not:4,4′-bis(N-acetyl-2-aminoethyl)diphenyldiazomethane,1-{2-[4-(diazo-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)phenyl phenyl diazomethane,bis-4,4′-N,N-dimethylamino diphenyldiazomethane,4-([3,4-dimethoxyphenyl]oxymethyl)phenyl phenyl diazomethane or4-([3-N,N-diethylaminophenyl]oxymethyl)phenyl phenyl diazomethane,

which process comprises oxidising a compound of the following formula(III):

wherein:

A is an aryl or heteroaryl ring;

y is 1, 2, 3, 4 or 5;

L_(A) is a single bond, -alk-, -arylene-, -alk-arylene-, -X-alk-,-X-alk-X-, -X-arylene-, X-arylene-X-, -X-alk-arylene-, -alk-X-arylene-,-alk-arylene-X, -X-alk-X-arylene-, -alk-X-arylene-X- or-X-alk-X-arylene-X-, wherein X is N(R″), O, or S and wherein alk isC₁₋₂₀ alkylene which is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl;

W_(A) is a group comprising an adhesive functional group or a groupwhich is a precursor of an adhesive functional group;

R is selected from hydrogen, aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above;

provided that when R is aryl or heteroaryl, said aryl or heteroaryl maybe unsubstituted or substituted by one, two, three, four or five groups,which groups are independently selected from C₁₋₆ alkyl, aryl, cyano,amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonicacid, sulfonyl and -L_(B)-W_(B), wherein L_(B) is as defined above forL_(A) and is the same as or different from L_(A), and W_(B) is asdefined above for W_(A) and is the same as or different from W_(A); and

provided that the compound is not:

4,4′-bis(N-acetyl-2-aminoethyl)benzophenone hydrazone,1-{2-[4-(hydrazono-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4,4-bis-N,N-dimethylamino benzophenone hydrazone,4-([3,4-dimethoxyphenyl]oxymethyl)benzophenone hydrazone,4-([3-N,N-diethylaminophenyl]oxymethyl)benzophenone hydrazone or4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)benzophenone hydrazone;

to produce a carbene precursor compound of formula (I).

Any suitable oxidant may be used. Suitable oxidants include metaloxides, such as mercuric oxide, nickel peroxide, or hydrogen peroxide orchlorine (bleach). Typically, the oxidant is mercuric oxide. Moretypically, this oxidation is conducted in the presence of a base, forinstance a metal hydroxide and sodium sulphate. The metal hydroxide istypically an alkali metal hydroxide, for instance potassium hydroxide. Asaturated solution of the metal hydroxide is generally used. The solventused for the metal hydroxide is suitably a polar protic solvent such asan alcohol, for instance ethanol. The solvent used for the solution ofthe compound of formula (III) is suitably a polar aprotic solvent, forinstance tetrahydrofuran (THF) or an ether.

Typically, R is selected from aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above, provided that R is not CF₃.

Typically, the compound of formula (I) is not4,4′-bis(N-acetyl-2-aminoethyl)diphenyldiazomethane,1-{2-[4-(diazo-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)phenyl phenyl diazomethane,bis-4,4′-N,N-dimethylamino diphenyldiazomethane,4-([3,4-dimethoxyphenyl]oxymethyl)phenyl phenyl diazomethane,4-([3-N,N-diethylaminophenyl]oxymethyl)phenyl phenyl diazomethane orbis-4,4′-tert-butyl ester diphenyldiazomethane.

Thus, typically, the compound of formula (III) is not4,4′-bis(N-acetyl-2-aminoethyl)benzophenone hydrazone,1-{2-[4-(hydrazono-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4,4-bis-N,N-dimethylamino benzophenone hydrazone,4-([3,4-dimethoxyphenyl]oxymethyl)benzophenone hydrazone,4-([3-N,N-diethylaminophenyl]oxymethyl)benzophenone hydrazone,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)benzophenone hydrazone or4,4′-bis-tert-butyl ester benzophenone hydrazone.

A compound of formula (I) in which W_(A) or W_(B) contains a groupselected from —OH and —NH(R″) can be further derivatised in order toproduce a compound of formula (I) in which W_(A) or W_(B) comprises thefollowing group:

in which Prot is a protecting group which is a precursor to a —CH═CH₂group; and X¹ is N(R″) or O, wherein R″ is selected from H, C₁₋₆ alkyland aryl.

Accordingly, in one embodiment of the process of the present inventionfor producing a carbene precursor compound of formula (I):

either W_(A) or W_(B) comprises a group selected from —OH and —NH(R″),wherein R″ is selected from H, C₁₋₆ alkyl and aryl,

and the process further comprises reacting said —OH or —NH(R″) withHal-C(O)-Prot, wherein Hal is a suitable leaving group and Prot is aprotecting group which is a precursor to a —CH═CH₂ group, to produce acarbene precursor compound of formula (I) in which either W_(A) or W_(B)comprises a functional group having the following structure:

wherein X¹ is N(R″) or O, wherein R″ and Prot are as defined above.Typically, Hal is a halo group, for instance Cl, Br or I. Alternatively,Hal may be any other suitable leaving group which, for reacting said —OHor —NH(R″) with Hal-C(O)-Prot, is functionally equivalent to a halogroup such as Cl, Br or I. When X¹ is O, a suitable leaving groupincludes any leaving group which gives an active ester.

Typically, the reaction is carried out in the presence of a base.Typically, the base is a Lewis base, for example an alkyl amine such astriethylamine. The reaction is typically carried out at a temperaturebelow room temperature, for example at about 0° C. The solvent used forthe reaction is typically an aprotic solvent, such as a hydrocarbon.Typically, toluene is used as the solvent.

The hydrazone compounds of formula (III) may be prepared by treating thecorresponding ketone compound with hydrazine in the presence of heat anda solvent. Accordingly, the present invention provides a process forproducing a compound of formula (III):

wherein:

A is an aryl or heteroaryl ring;

y is 1, 2, 3, 4 or 5;

L_(A) is a single bond, -alk-, -arylene-, -alk-arylene-, -X-alk-,-X-alk-X-, -X-arylene-, X-arylene-X-, -X-alk-arylene-, -alk-X-arylene-,-alk-arylene-X, -X-alk-X-arylene-, -alk-X-arylene-X- or-X-alk-X-arylene-X-, wherein X is N(R″), O, or S and wherein alk isC₁₋₂₀ alkylene which is optionally interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁ alkyl or aryl;

W_(A) is a group comprising an adhesive functional group or a groupwhich is a precursor of an adhesive functional group;

R is selected from hydrogen, aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl andC₁₋₆ alkyl, which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S orarylene wherein R″ is as defined above;

provided that when R is aryl or heteroaryl, said aryl or heteroaryl maybe unsubstituted or substituted by one, two, three, four or five groups,which groups are independently selected from C₁₋₆ alkyl, aryl, cyano,amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆alkoxy, aryloxy, haloalkyl, thiol, arylthio, sulfonic acid, sulfonyl and-L_(B)-W_(B), wherein L_(B) is as defined above for L_(A) and is thesame as or different from L_(A), and W_(B) is as defined above for W_(A)and is the same as or different from W_(A); and

provided that the compound is not:

4,4′-bis(N-acetyl-2-aminoethyl)benzophenone hydrazone,1-{2-[4-(hydrazono-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4,4-bis-N,N-dimethylamino benzophenone hydrazone,4-([3,4-dimethoxyphenyl]oxymethyl)benzophenone hydrazone,4-([3-N,N-diethylaminophenyl]oxymethyl)benzophenone hydrazone or4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)benzophenone hydrazone;

the process comprising treating a compound of formula (IV) withhydrazine in the presence of heat:

wherein R, A, L_(A), W_(A), and y are as defined above.

Typically, hydrazine is used in the form of hydrazine hydrate.Typically, the compound of formula (IV) is treated with hydrazine in thepresence of heat and a solvent. Any suitable solvent may be employed,for instance a polar protic solvent such as an alcohol. Typically, thesolvent is methanol or ethanol. The reaction is carried out withheating, typically at the reflux temperature of the solvent used. Forexample, when the solvent is ethanol the reaction is suitably carriedout at a temperature of 78° C. or higher, e.g. at a temperature of 80°C.

Typically, R is selected from aryl, heteroaryl, C₁₋₁₀ alkoxy, aryloxy,di(C₁₋₁₀)alkylamino, alkylarylamino, diarylamino, C₁₋₁₀ alkylthio,arylthio and CR′₃, wherein each R′ is independently selected from ahalogen atom, aryl, heteroaryl, C₃₋₇ C₅₋₇ heterocyclyl and C₁₋₆ alkyl,which C₁₋₆ alkyl is optionally interrupted by N(R″), O, S or arylenewherein R″ is as defined above, provided that R is not CF₃.

Typically, the compound of formula (III) is not4,4′-bis(N-acetyl-2-aminoethyl)benzophenone hydrazone,1-{2-[4-(hydrazono-phenyl-methyl)-benzyloxy]-ethyl}-3-phenyl urea,4,4-bis-N,N-dimethylamino benzophenone hydrazone,4-([3,4-dimethoxyphenyl]oxymethyl)benzophenone hydrazone,4-([3-N,N-diethylaminophenyl]oxymethyl)benzophenone hydrazone,4-([N-ethyl-N-phenyl-2-aminoethyl]oxymethyl)benzophenone hydrazone or4,4′-bis-tert-butyl ester benzophenone hydrazone.

The ketone compounds of formula (IV):

in which R, A, L_(A), W_(A), and y are as defined above, may be preparedfrom commercially available starting materials using known syntheticprocedures.

For example, many compounds of formula (IV) can be prepared by analogywith the syntheses outlined in the Examples for the ketone compounds4-hydroxylmethyl benzophenone (3), 4-(allyloxymethyl)benzophenone (9)and 4-(Benzoyl benzyl)phosphonic acid diethyl ester (14). Each of thosecompounds was synthesised starting from 4-methyl benzophenone (1), whichis commercially available. That compound was brominated to yield4-bromomethyl benzophenone (2), which was subsequently converted intoeither 4-hydroxymethyl benzophenone (3) (by treatment of 2 with anaqueous solution of a base) or 4-(Benzoyl benzyl)phosphonic acid diethylester (14) (by treatment of 2 with triethyl phosphate).4-(allyloxymethyl)benzophenone (9) was synthesised by treating4-hydroxymethyl benzophenone (3) with sodium hydride and allyl bromide.

Many other ketone compounds of formula (IV) in which A is phenyl and Ris substituted or unsubstituted phenyl may be synthesised starting frombenzophenone (which is commercially available) or from a substitutedderivative of benzophenone. Many substituted derivatives of benzophenoneare commercially available and/or easily synthesised using knownmethods. Examples of commercially available substituted benzophenonecompounds are 2-hydroxybenzophenone, 4-hydroxybenzophenone,3-bromobenzophenone, 4-bromobenzophenone, 2-cyanobenzophenone,4-cyanobenzophenone, 2-aminobenzophenone, 3-nitrobenzophenone,4-nitrobenzophenone, and 2-ethylbenzophenone. Thus, compounds of formula(IV) in which A is phenyl and R is a substituted phenyl group may besynthesised starting from the corresponding substituted benzophenonecompound. Alternatively, the (substituted) benzophenone system could besynthesised using standard synthetic approaches, for example, byFriedel-Crafts reactions or variants and equivalents thereof, or byaddition of an aromatic carbanion equivalent to an aldehyde followed byoxidation, or by oxidation of a suitable substituted diarylmethane.

The one or more -L_(A)-W_(A) groups may be introduced by analogy withthe syntheses of compounds 3, 9 and 14 in the Examples, or by any othersuitable synthetic procedure. For example, one or more suitable leavinggroups may be introduced at the position(s) of a benzophenone orsubstituted benzophenone compound at which -L_(A)-W_(A) substitution isdesired. The leaving group may be a halo group, for example bromo. Theleaving group may be introduced directly onto a phenyl ring of thebenzophenone compound (e.g. as in 4-bromobenzophenone) or onto a phenylring substituent, such as an alkyl group (e.g. as in 4-methylbenzophenone). Following introduction of the one or more leaving groups,the leaving group(s) may be substituted by one or more -L_(A)-W_(A)groups. Thus, for example, a bromo leaving group could be substituted bya hydroxyl group or a phosphonic acid ester group. Alternatively, one ormore functional groups may be introduced at the position(s) of abenzophenone or substituted benzophenone compound at which -L_(A)-W_(A)group(s) are desired. The functional group(s) may then be converted intothe -L_(A)-W_(A) group(s). For example, an aldehyde substituent on aphenyl ring may be treated with a phosphorus ylide (Wittig reaction) toyield a styryl group.

Where R is aryl or heteroaryl and one or more -L_(B)-W_(B) groups aredesired, these groups may be introduced by analogy with the syntheticmethods used to introduce the one or more -L_(A)-W_(A) groups.

Compounds of formula (IV) in which A or R is heteroaryl may besynthesised starting from ketone compounds which include a heteroarylring. Many ketone compounds including a heteroaryl ring are commerciallyavailable and/or easily synthesised. Examples of such commerciallyavailable compounds are 2-benzoylpyridine, di-2-pyridyl ketone and2-benzoylthiophene.

Ketone compounds of formula (IV) in which R is other than aryl orheteroaryl may be synthesised starting from the appropriate ketoneR^(B)C(═O)R^(A), wherein R^(A) is aryl or heteroaryl and R^(B) isselected from hydrogen, C₁₋₁₀ alkoxy, aryloxy, di(C₁₋₁₀)alkylamino,alkylarylamino, diarylamino, C₁₋₁₀ alkylthio, arylthio and CR′₃, whereineach R′ is independently selected from a halogen atom, aryl, heteroaryl,C₃₋₇ cycloalkyl, C₅₋₇ heterocyclyl and C₁₋₆ alkyl, which C₁₋₄ alkyl isoptionally interrupted by N(R″), O, S or arylene wherein R″ is H, C₁₋₄alkyl or aryl. Examples of such commercially available ketones includebenzaldehyde, 2,2-Dimethylpropiophenone (i.e. tert-Butyl phenyl ketone)and 2,2,2-trifluoroacetophenone.

In the carbene precursor compounds of the invention, of formula (I), inthe process of the invention for producing a carbene precursor compoundof formula (I), and in the process of the invention for producing acompound of formula (III), -L_(A)-W_(A) and, where present,-L_(A)-W_(B), are typically other than —NMe₂.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other than—N═N—Ar^(P), wherein Ar^(P) is an unsubstituted or substituted phenylgroup. Typically, Ar^(P) is:

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other than—CH₂OR^(QQ) wherein R^(QQ) is N-ethyl-N-phenyl-2-aminoethyl,3,4-dimethoxyphenyl or 3-N,N-dimethylaminophenyl.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other than—N⁺Me₂O⁻.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other than—CH₂O(CH₂)₂N(H)C(O)N(H)Ph.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-Ws, are other than—CH₂O(CH₂)₂N(Ph)CH₂CH₃.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other thanhydrogen.

More typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are otherthan each of the following moieties:

—CH₂OR^(QQ) wherein R^(QQ) is N-ethyl-N-phenyl-2-aminoethyl,3,4-dimethoxyphenyl or 3-N,N-dimethylaminophenyl;

—NMe₂;

—N⁺Me₂O⁻;

—CH₂O(CH₂)₂N(H)C(O)N(H)Ph;

—CH₂O(CH₂)₂N(Ph)CH₂CH₃; and

—N═N—Ar^(P), wherein Ar^(P) is an unsubstituted or substituted phenylgroup. Typically, Ar^(P) is:

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other thanhydrogen and other than Q^(P), wherein:

Q^(P) is selected from N(Z₁ ^(P))(Z₂ ^(P)) andCH₂—V^(P)—(W^(P)—R^(P))_(a);

Z₁ ^(P) and Z₂ ^(P) are independently selected from aryl which isunsubstituted or substituted, heteroaryl which is unsubstituted orsubstituted, C₁₋₁₀ alkoxy which is unsubstituted or substituted, C₁₋₁₀alkylamino which is unsubstituted or substituted, di(C₁₋₁₀)alkylaminowhich is unsubstituted or substituted, C₁₋₁₀ alkylthio which isunsubstituted or substituted, and C₁₋₁₀ alkyl which is unsubstituted orsubstituted and which is optionally interrupted by N(R^(2P)), O or Swherein R^(2P) is H or C₁₋₆ alkyl;

V^(P) is C₁₋₁₀ alkylene, —O—C₁₋₁₀ alkylene-, —C₁₋₁₀ alkylene-O— or—O-C₁₋₁₀ alkylene-O—;

W^(P) is a functional group of one of the following formulae (a) to (c):

wherein X^(P) is O, S or NH₂ ⁺;

R^(P) is selected from H, C₁₋₆ alkyl which is unsubstituted orsubstituted, aryl which is unsubstituted or substituted and heteroarylwhich is unsubstituted or substituted; and

a is 1, 2 or 3.

Typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are other thanhydrogen and other than —CH₂OR^(Q), wherein:

R^(Q) is Ar^(1Q) or (CH₂)_(b)(NR^(1Q))(R^(2Q));

Ar^(1Q) is:

wherein Y^(Q) is C₁₋₄ alkoxy or NR^(3Q)NR^(4Q));

R^(3Q) and R^(4Q), which may be the same or different, are C₁₋₄ alkyl;

c is 0 or an integer of 1 to 3;

R^(1Q) is C₁₋₄ alkyl;

R^(2Q) is phenyl; and

b is an integer of 1 to 4.

More typically, -L_(A)-W_(A) and, where present, -L_(A)-W_(B), are otherthan hydrogen and other than Q^(P) and other than —CH₂OR^(Q), whereinQ^(P) and R^(Q) are as defined above.

The present invention is further illustrated in the Examples whichfollow:

EXAMPLES

[4-(Diazo(phenyl)methyl)phenyl]methanol (5) and7-Oxa-bicyclo[2.2.1]hept-5-ene-2-carboxylicacid-4-(diazo-phenylmethyl)-benzyl ester (7) were prepared and polymerswere functionalised as shown in Scheme 1.

Reference Example 1 Preparation of 4-Bromomethyl benzophenone (2)

A stirred mixture of 4-methyl benzophenone (1) (15.0 g, 76 mmol) andN-bromo succinimide (14.2 g, 80 mmoll) in chloroform (100 ml) was heatedto reflux for 18 h. with a 100W bulb shining 2 cm from the flask. Thereaction mixture was cooled, washed with water and concentrated invacuo. The resulting solid was washed with diethyl ether to leave 2(15.1 g, 72%) as a white solid; δ_(H) (CDCl₃) 4.55 (2H, s, CH₂Br),7.46-7.84 (9H, m, Ar—H).

Reference Example 2 Preparation of 4-Hydroxylmethyl benzophenone (3)

To a suspension of 2 (6.0 g, 22 mmol) in a mixture of 1,4 dioxane (60ml) and water (60 ml) was added calcium carbonate (10.8 g, 110 mmol).The mixture was heated to reflux for 18 h, concentrated in vacuo and theresidue portioned between DCM and water. The organic layer wascollected, dried over MgSO₄, concentrated in vacuo then recrystalisedfrom diethyl ether to furnish 3 (4.1 g, 89%) as a white solid; M.P.59-61° C. (Lit 61-64° C.); δ_(H) (CDCl₃) 3.14 (s, 1H, CH₂OH), 4.75 (s,2H, CH₂OH), 7.41-7.49 (m, 4H, 3-, 3′-, 5-, 5′-H), 7.54-7.58 (m, 1H,4′-H), 7.72-7.76 (m, 4H, 2-, 2′-, 6-, 6′-H) ppm; δ_(C) (CDCl₃) 64.4(CH₂OH), 126.4 (3′-, 5′-C), 128.3 (3-, 5-C), 130.0, 130.4 (2-, 2′-, 6-,6′-C), 132.5 (4′-C), 136.4, 137.5 (1-, 1′-C), 140.0 (4-C), 196.9(Ar₂C═O) ppm; ν_(max) (thin film) 3406, 3058, 2921, 1655, 1279 cm⁻¹; m/z(ES) 211 ([M−H]⁻ 100%), 183 (45%).

Example 1 Preparation of [4-(Diazo(phenyl)methyl)phenyl]methanol (5)4-Hydroxymethyl benzophenone hydrazone (4)

4-Bromomethyl benzophenone (2) was prepared as described in ReferenceExample 1. 4-Bromomethyl benzophenone (2) was converted into4-Hydroxylmethyl benzophenone (3) as described in Reference Example 2.To solution of 3 (2.5 g, 12 mmol) in ethanol (20 ml) was added hydrazinehydrate (2.9 g 59 mmol). The mixture was heated to reflux for 24 h. thenconcentrated in vacuo. The residue was portioned between DCM and waterand the organic layer collected and concentrated to yield 4 (2.6 g, 98%)a mixture of cis and trans isomers and as a yellow semi solid; δ_(H)(CDCl₃) 2.84, 3.09 (2×bs, 1H, OH), 4.51, 4.61 (2×s, 2H, CH₂OH), 5.32(bs, 2H, NNH₂), 7.13-7.17 (m, 4H, 3-, 3′-, 5-, 5′-H), 7.30-7.43 (m, 5H,2-, 2′-, 4′-, 6-, 6′-H) ppm; δ_(C) (CDCl₃) 64.4, 64.6 (2×CH₂OH), 126.4,126.6, 127.7, 128.0, 128.1, 128.6, 128.8, 128.9, 129.3 (Ar—C), 131.8,132.7 (2×1′-C), 137.5, 138.2 (2×1-C), 141.0, 141.8 (2×4′-C), 149.2 (C═N)ppm; ν_(max) (thin film) 3384, 2870, 1583, 1444, 1412, 1015 cm⁻¹; found(ES) 227.1180, C₁₄H₁₅N₂O requires 227.1179.

[4-(Diazo(phenyl)methyl)phenyl]methanol (5)

To a mixture of mercury (II) oxide (2.9 g, 13 mmol), sodium sulphate(2.2 g, 15 mmol) and sat potassium hydroxide in ethanol (4 ml) was addeda solution of 4 (2.6 g, 11 mmol) in dry THF (20 ml). The mixture wasstirred in the dark for 2 h. then filtered through a celite pad.Concentration of the filtrate in vacuo yielded 5 (2.4 g, 100%) as a darkred oil; δ_(H) (CDCl₃) 4.69 (s, 2H, CH₂OH), 7.29-7.31 (m, 4H, 3-, 3′-,5-, 5′-H), 7.39-7.41 (m, 5H, 2-, 2′-, 4′-, 6-, 6′-H) ppm; δ_(C) (CDCl₃)64.8 (CH₂OH), 125.1, 125.2 (3-, 3′-, 5-, 5′-C), 125.6 (4′-C), 127.9,129.1 (2-, 2′-, 6-, 6′-C), 128.9, 129.4 (1-, 1′-C), 138.2 (4-C) ppm;ν_(max) (thin film) 3346, 2872, 2038, 1511, 1493 cm⁻¹; m/z (F14) 224([M]⁺, 100%); found (FT) 224.0949, C₁₄H₁₂N₂O requires 224.0950.

Example 2 Preparation of hydroxy polymer (6)

[4-(Diazo(phenyl)methyl)phenyl]methanol (5) was prepared as described inExample 1. A solution of 5 in THF was coated onto the polymer and toheated to 120° C. for 10 mins, then washed with acetone to yield thehydroxyl functionalised polymer 6.

Example 3 Preparation of 7-Oxa-bicyclo[2.2.1]hept-5-ene-2-carboxylicacid-4-(diazo-phenylmethyl)-benzyl ester (7)

[4-(Diazo(phenyl)methyl)phenyl]methanol (5) was prepared as described inExample 1. To a solution of 5 (5 g, 22 mmol) in dry toluene (50 ml) anddry triethylamine (6.7 g, 66 mmol) at 0° C. was added a solution of7-oxabicyclo[2.2.1]heptane-2-carbonyl chloride (7.0 g, 44 mmol) in drytoluene. The mixture was stirred at 0° C. for 2 h. then quenched withsat. aqueous sodium carbonate (50 ml). The organic layer was separatedand dried over MgSO₄ to yield 7 as a red solution in toluene.

Example 4 Preparation of acrylate polymer (8)

7-Oxa-bicyclo[2.2.1]hept-5-ene-2-carboxylicacid-4-(diazo-phenylmethyl)-benzyl ester (7) was prepared as describedin Example 3. A solution of 7 in toluene was coated onto the polymer andheated to 120° C. for 15 mins, then washed with acetone to yield theacrylate functionalised polymer 8.

1-(allyloxymethyl)-4-(diazo(phenyl)methyl)benzene (11) was prepared andpolymers were functionalised as shown in Scheme 2.

Example 5 Preparation of1-(allyloxymethyl)-4-(diazo(phenyl)methyl)benzene (11)4-(Allyloxymethyl)benzophenone (9)

4-Bromomethyl benzophenone (2) was prepared as described in ReferenceExample 1. 4-Bromomethyl benzophenone (2) was converted into4-Hydroxylmethyl benzophenone (3) as described in Reference Example 2.To a solution of 3 (0.5 g, 3.4 mmol) in dry THF (10 ml) was added sodiumhydride (0.3 g, 60% dispersion in mineral oil, 6.7 mmol). The mixturewas stirred for 5 min, then allyl bromide (0.8 g, 6.7 mmol) was added.The mixture as stirred for 18 h. the quenched with water andconcentrated in vacuo. The residue was portioned between DCM and water,the organic layer collected, dried over MgSO₄ and concentrated. Amineral oil impurity was removed using a silica plug eluting with petrolthen ethyl acetate to yield 9 (0.6 g, 92%) as a yellow oil; δ_(H)(CDCl₃) 4.08 (dt, 2H, J=1.4, 5.5 Hz, OCH₂CH═CH₂), 4.60 (s, 2H, ArCH₂O),5.24 (ddt 1H, J=1.4, 3.2, 10.3 Hz, OCH₂CH═CHH), 5.34 (ddt 1H, J=1.4,3.2, 17.3 Hz, OCH₂CH═CHH), 5.88-6.08 (m, 1H, OCH₂CH═CHH), 7.42-7.50 (m,4H, 3-, 3′-, 5-, 5′-H), 7.54-7.62 (m, 1H, 4′-H), 7.78-7.82 (m, 4H, 2-,2′-, 6-, 6′-H) ppm; δ_(C) (CDCl₃) 61.4, 71.3 (ArCH₂O, OCH₂CH═CH₂), 117.3(OCH₂CH═CH₂), 127.0, 128.1 (3-, 3′-, 5-, 5′-C), 129.8, 130.1 (2-, 2′-,6-, 6′-C), 132.2 (4′-C), 134.3 (OCH₂CH═CH₂), 136.6, 137.5 (1-, 1′-C),143.1 (4-C), 196.2 (C═O) ppm; ν_(max) (thin film) 3061, 2855, 1658,1609, 1447, 1412, 1278, 1089, 924 cm⁻¹; m/z (Er) 252 ([M⁺], 85%), 222(100%); found 252.1158, C₁₇H₁₆O₂ requires 252.1150.

[(4-(Allyloxylmethyl)phenyl)(phenyl)methylene]hydrazine (10)

To solution of 9 (1.09 g, 43 mmol) in methanol (10 ml) was addedhydrazine hydrate (1.08 g 20 mmol). The mixture was heated to reflux for48 h. then concentrated in vacuo. The residue was partioned between DCMand water and the organic layer collected and concentrated to yield 10(1.10 g, 98%) as a mixture of cis and trans isomers and as a yellow oil;δ_(H) (CDCl₃) 4.03, 4.13 (2×dt, 2H, J=1.4, 5.6 Hz, OCH₂CH═CH₂) 4.52,4.60 (2×s, 2H, ArCH₂O), 5.20, 5.27 (ddd, 1H, J=1.4, 3.0, 10.4 Hz,OCH₂CH═CHH), 5.32, 5.37 (ddd, 1H, J=1.4, 3.2, 17.3 Hz, OCH₂CH═CHH), 5.45(bs, 2H, NNH₂), 5.91-6.06 (m, 1H, OCH₂CH═CH₂), 7.28-7.31 (m, 4H, 3-,3′-, 5-, 5′-H), 7.46-7.55 (m, 5H, 2-, 2′-, 4′-, 6-, 6′-H) ppm; δ_(C)(CDCl₃) 60.1, 71.5, 71.7 (ArCH₂O, OCH₂CH═CH₂), 117.0, 117.3(OCH₂CH═CH₂), 126.3, 126.4, 127.4, 128.0, 128.5, 128.7, 129.3 (Ar—C),134.4, 134.6 (2×OCH₂CH═CH₂), 137.7, 138.1, 139.1 (Ar—C), 148.7 (C═N)ppm; ν_(max) (thin film) 3404, 3289, 3057, 2855, 1612, 1444, 1411, 1277,1083 cm⁻¹; m/z (ES⁺) 267 ([M+H]⁺, 100%); found (EST⁺) 267.1492,C₁₇H₁₉N₂O requires 267.1492.

1-(allyloxymethyl)-4-(diazo(phenyl)methyl)benzene (11)

To a mixture of mercury (II) oxide (3.1 g, 14 mmol), sodium sulphate(2.4 g, 16 mmol) and sat potassium hydroxide in ethanol (3 ml) was addeda solution of 10 (3.2 g, 12 mmol) in dry TIM (20 ml). The mixture wasstirred in the dark for 2 h. then filtered through a celite pad.Concentration of the filtrate in vacuo yielded 11 (3.1 g, 100%) as adark red oil; δ_(H) (CDCl₃) 3.90-3.94 (m, 2H, OCH₂CH═CH₂), 4.38 (s, 2H,ArCH₂O), 5.05-5.26 (m, 2H, OCH₂CH═CH₂), 5.74-5.94 (m, 1H, OCH₂CH═CH₂),7.12-7.36 (m, 9H, Ar—H) ppm; δ_(C) 71.0, 71.6 (OCH₂CH═CH₂, ArCH₂O),117.0 (OCH₂CH═CH₂), 124.9, 125.0, 125.4, 128.5, 129.0 (Ar—C), 129.8,130.1 (1-, 1′-C), 134.5 (OCH₂CH═CH₂), 135.6 (4-C) ppm; ν_(max) (thinfilm) 3029, 2855, 2038, 1596, 1512, 1494, 1085 cm⁻¹; m/z (Fr) 264 ([M]⁺,70%), 252 (100%), 196 (35%); found (Fr) 264.1250, C₁₇H₁₆N₂O requires264.1263.

Example 6 Preparation of olefin polymer (12)

1-(allyloxymethyl)-4-(diazo(phenyl)methyl)benzene (11) was prepared asdescribed in Example 5. A solution of 11 in THF was coated onto thepolymer and heated to 120° C. for 15 mins, then washed with acetone toyield the olefin functionalised polymer 12.

Example 7 Preparation of epoxide polymer (13)

Olefin functionalised polymer 12 was prepared as described in Example 6.To a flask containing the olefin functionalised polymer 12 was added asolution of meta-chloroperbenzoic acid in DCM. The polymer was soakedfor 20 h. then filtered and washed with DCM and water to yield theepoxide functionalised polymer 13.

[4-(Diazo-phenyl-methyl)-benzyl]phosphonic acid diethyl ester (16) wasprepared and polymers were functionalised as shown in Scheme 3.

Example 8 Preparation of [4-(Diazo-phenyl-methyl)-benzyl]phosphonic aciddiethyl ester (16) 4-(Benzoyl benzyl)phosphonic acid diethyl ester (14)

4-Bromomethyl benzophenone (2) was prepared as described in ReferenceExample 1. A solution of 2 (7.8 g, 28 mmol) in triethyl phosphite (20ml) was heated to reflux for 4 h. then concentrated in vacuo. Theresidue was purified by flash chromatography on silica gel eluting with65% ethyl acetate: petrol to yield 14 (8.1 g, 86%) as a pale yellow oil;8H (CDCl₃) 1.24 (6H, dt, J_(H-H)=7.1 Hz, J_(H-P)=3.6 Hz, 2×CH₂CH₃), 3.22(2H, d, J_(H-P)=22.1 Hz, ArCH₂P), 4.04 (4H, q, J_(H-H, H-P)=7.1 Hz,2×CH₂CH₃), 7.47-7.78 (9H, m, Ar—H) ppm; δ_(C)(CDCl₃) 16.4 (d,J_(C-P)=4.9 Hz, 2×CH₂CH₃), 33.9 (d, J_(C-P)=137.5 Hz, ArCH₂P), 62.3 (d,J_(C-P)=7.0 Hz, 2×CH₂CH₃), 128.3 and 129.7 (3-, 5-, 3′-, 5′-C), 130.3and 132.3 (2-, 6-, 2′-, 6′-C), 132.4 (4′-C), 136.1 and 136.7 (1-, 1′-C),137.5 (4-C), 196.2 (Ar₂CO) ppm; δ_(P) (CDCl₃) 26.47 ppm; ν_(max) (thinfilm) 2984 (C—H_(st)), 1657 (C═O_(st)), 1278 (P═O_(st)), 1026 (P—O_(st))cm⁻¹; m/z (ES) 333 ([M+H]⁺5%), 355 ([M+Na]⁺10%), 391([M+NH₄+MeCN]⁺100%), 687 ([M2+Na]⁺ 30%).

[4-(Hydrazono-phenyl-methyl)-benzyl]phosphonic acid diethyl ester (15)

To solution of 14 (2.2 g, 6.6 mmol) in methanol (20 ml) was addedhydrazine hydrate (10 ml). The mixture was heated to reflux for 6 h.then concentrated in vacuo. The residue was portioned between DCM andwater and the organic layer collected and concentrated to yield 15 (2.3g, 100%) as a mixture of cis and trans isomers and as a yellow oil;δ_(H) (CDCl₃) 1.23 (6H, dt, J_(H-H)=7.1 Hz, J_(H-P)=3.0 Hz, 2×CH₂CH₃),1.27 (6H, dt, J_(H-H)=7.1 Hz, J_(H-P)=3.0 Hz, 2×CH₂CH₃′), 3.12 (2H, d,J_(H-P)=17.6 Hz, ArCH₂P), 3.23 (2H, d, J_(H-P)=17.6 Hz, ArCH₂P′), 4.08(4H, m, 2×CH₂CH₃), 5.44 (2H, bs, NH₂), 7.47-7.78 (9H, m, Ar—H) ppm;δ_(C) (CDCl₃) 16.3 (d, J_(C-P)=6.0 Hz, 2×CH₂CH₃), 16.4 (d, J_(C-P)=6.2Hz, 2×CH₂CH₃′), 33.4 (d, J_(C-P)=137.9 Hz, ArCH₂P), 33.4 (d,J_(C-P)=138.9 Hz, ArCH₂P′), 62.1 (m, 2×CH₂CH₃), 126.4-138.4 (Ar—C),148.3 and 148.4 (Ar₂CNNH₂) ppm; δ_(P) (CDCl₃) 26.04, 26.26 ppm; ν_(max)(thin film) 3387 (N—H_(st)), 2983 (C—H_(st)), 1611 (C═N_(st)), 1234(P═O_(st)), 1023 (P—O_(st)); m/z (ES⁺) 347.16 ([M+H]⁺60%), 26919([M+Na]⁺60%), 405.28 ([M+NH₄+MeCN]⁺100%); found (ES) 347.1541,C₁₈H₂₄N₂O₃P requires 347.1525.

[4-(Diazo-phenyl-methyl)-benzyl]phosphonic acid diethyl ester (16)

To a mixture of mercury (II) oxide (0.21 g, 0.97 mmol), sodium sulphate(0.16 g, 1.1 mmol) and sat potassium hydroxide in ethanol (0.2 ml) wasadded a solution of 15 (0.28 g, 0.81 mmol) in dry THF (20 ml). Themixture was stirred in the dark for 1 h. the filtered through a celitepad. Concentration of the filtrate in vacuo yielded 16 (0.25 g, 89%) asa dark red oil; δ_(H) (CDCl₃) 1.28 (6H, d, J_(H-H)=7.1 Hz, 2×CH₂CH₃),3.16 (2H, d, J_(H-P)=21.7 Hz, ArCH₂P), 3.98-4.13 (4H, m, 2×CH₂CH₃),7.15-7.43 (9H, m, Ar—H) ppm; δ_(C) (CDCl₃) 16.4 (d, J_(C-P)=6.0 Hz,2×CH₂CH₃), 33.3 (d, J_(C-P)=138.2 Hz, ArCH₂P), 62.1 (d, J_(C-P)=6.8 Hz,2×CH₂CH₃), 125.1, 125.2, 125.2, 125.6, 129.1 (Ar—C), 129.4 (4-C), 130.4and 130.5 (1-, 1′-C) ppm; δ_(P) (CDCl₃) 26.37 ppm; ν_(max) (thin film)2982 (C—H_(st)), 2039 (C═N=N_(st)), 1248 (P═O_(st)), 1027 (P—O_(st))cm⁻¹; m/z (ES⁺) 403 ([M+NH₄+MeCN]⁺100%); found (FI⁺) 344.1778,C₁₈H₂₁N₂O₃P requires 344.1290.

Example 9 Preparation of phosphonate ester polymer (17)

[4-(Diazo-phenyl-methyl)-benzyl]phosphonic acid diethyl ester (16) wasprepared as described in Example 8. A solution of 16 in DCM was coatedonto the polymer and heated to 100° C. for 10 mins, then washed with DCMto yield the functionalised polymer 17.

Example 10 Preparation of phosphonic acid polymer (18)

Phosphonate ester polymer (17) was prepared as described in Example 9.To a flask containing the polymeric phosphonate ester 17 was added 1Mhydrochloric acid. The mixture was stirred for 18 h., filtered and thepolymer washed with water to yield polymeric phosphonic acid 18.

Example 11 Preparation of phosphonic acid calcium salt polymer (19)

Polymeric phosphonic acid 18 was immersed in an aqueous calciumhydroxide solution for 6 h., then washed with water to yield polymericphosphonic acid calcium salt 19.

Example 12 Coating and Adhesion of 6 and 8

To a sample of treated polymer (6 or 8) was added the required coating.A second sheet of unfunctionalised polymer was placed on top and thelaminate was flattened using a roller. The composite material was cured(using heat and/or light), the sheets separated and the coating testedfor adhesion using a tape test and a cross hatch tape test.

TABLE 2 Tape Test and Cross Hatch Test results for 6 and 8 Cross HatchTest System Coating Conditions Tape Test Test 1 6 Laromer UVCure, thenPass Pass 5000 140° C. 5 min 2 6 Cationic UV Cure Pass Pass coatingmixture 1 3 8 Acrylate UV Cure Pass Fail coating mixture 2

The last two tests (Tests 2 and 3) were repeated on blank material, andin both cases the result was a fail. Based on experienced, the firsttest (Test 1) would also have failed had it been repeated using blankmaterial.

Description of the Tape Test:

The treated polymers were taped with a strip of adhesive tape. In eachcase the tape was secured by rubbing down with an appropriate smoothedged tool, and the strip was then rapidly pulled off. A “Pass” occurswhen the top laminate layer remains fast.

Description of the Cross Hatch Test:

The treated polymers were scratched with a sharp blade in a series of“X” marks, and then taped with a strip of adhesive tape. In each casethe tape was secured by rubbing down with an appropriate smooth edgedtool, and the strip was then rapidly pulled off. A “Pass” occurs whenthe top laminate layer remains fast.

A full description of the Tape Test and Cross Hatch test is given inASTM D3359, which describes a standard method for the application andperformance of these tests.

Example 13 Biocompatibility Against MG63 Human Osteosarcoma Cell Line

AlamarBlue™ Proliferation Study:

Cells were seeded at 5×10³ cells per 10×10 mm membrane and left toculture for a 2-week period. Within this period of in vitro culture, theAlamarBlue™ assay was performed at day 5, day 8 and day 13 time points.The study was carried out on unmodified Hybond-N polymer membrane(control), as well as on a Hybond-N membrane functionalised withphosphonic acid (18) and a Hybond-N membrane functionalised withphosphonic acid calcium salt (19). The results are shown in FIG. 1, inwhich the control is denoted “C”, and in the following Table 3. Thephosphonic acid-functionalised Hybond-N (18) was prepared as describedin Examples 9 and 10, using a Hybond-N membrane as the polymer. Thephosphonic acid calcium salt-functionalised Hybond-N (19) was preparedas described in Examples 9, 10 and 11 using a Hybond-N membrane as thepolymer.

TABLE 3 Results of AlamarBlue ™ proliferation study on unmodifiedHybond-N polymer (control) and modified Hybond-N polymer (18 and 19)Control/(Average 18/(Average 19/(Average Time/days RFU value) RFU value)RFU value) 5 1233.64 496.07 557.38 8 1962.44 1092.87 1961.33 13 3042.343288.06 3896.38

The invention claimed is:
 1. A carbene precursor compound of thefollowing formula (I):

wherein: A is an aryl or heteroaryl ring; y is 1 or 2; L_(A) is -alk-,-arylene-, -alk-arylene-, -alk-X-arylene-, -alk-arylene-X, or-alk-X-arylene-X-, wherein X is N(R″), O, or S and wherein alk is C₁₋₂₀alkylene which is uninterrupted or interrupted by N(R″), O, S orarylene, wherein R″ is H, C₁₋₆ alkyl or aryl; W_(A) is a groupcomprising an adhesive functional group or a group which is a precursorof an adhesive functional group, wherein W_(A) is: a group selectedfrom: -L²—OH, -L²—NH₂, -L²—SH, C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀heterocyclyl, aryl and heteroaryl, wherein said C₁₋₂₀ alkyl, C₃₋₂₀cycloalkyl, C₃₋₂₀ heterocyclyl, aryl and heteroaryl are each substitutedby -L²—OH, -L²—NH₂ or -L²—SH, wherein said C₁₋₂₀ alkyl is uninterruptedor interrupted by N(R″), O, S or arylene, wherein R″ is H, C₁₋₆ alkyl oraryl, and wherein L² is a single bond, C₁₋₆ alkylene, arylene,-arylene-C₁₋₆ alkylene- or -C₁₋₆ alkylene-arylene-, wherein each of saidC₁₋₆ alkylene groups is uninterrupted or interrupted by N(R″), O, S orarylene; a group which comprises a plurality of —OH, —NH₂ or —SHmoieties; a group which comprises at least one aliphatic carbon-carbondouble bond; a group which comprises at least one epoxide group; a groupwhich comprises one or more of any one of the following groups: aphosphonic acid group or a salt thereof, a sulfonic acid group or a saltthereof, a carboxylic acid group or a salt thereof, a sulfonamide group,and C(O)NH₂; a group which comprises at least one group having thestructure:

wherein X¹ is a single bond, C(R″)(R′″), N(R″) or O, wherein R″ and R′″are independently selected from H, C₁₋₆ alkyl or aryl, and wherein Protis a protecting group which is a precursor to a —CH═CH₂ group, whereinProt is selected from 7-oxabicyclo[2.2.1]hept-2-yl, an organometallicgroup, and a 1,2-dioxygenated substrate; or a group which comprises-P(═O)(OR⁴)₂ or

wherein R⁴ is C₁₋₆ alkyl or aryl; and Y is H, C₁₋₆ alkyl, aryl, —OH, —SHor NH₂; R is selected from aryl, heteroaryl and H; provided that when Ris aryl or heteroaryl, said aryl or heteroaryl may be unsubstituted orsubstituted by one or two groups, which groups are independentlyselected from C₁₋₆ alkyl, aryl, cyano, amino, keto, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,hydroxy, halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, haloalkyl, thiol,C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl and -L_(B)-W_(B),wherein L_(B) is as defined above for L_(A) and is the same as ordifferent from L_(A), and W_(B) is as defined above for W_(A) and is thesame as or different from W_(A).
 2. A compound according to claim 1wherein W_(A) and W_(B) are independently selected from:

-L²-OH, -L²-NH₂,-L²-SH, -L²-M, C₁₋₂₀ alkyl, C₃-₂₀ cycloalkyl, C₃₋₂₀heterocyclyl, aryl and heteroaryl, wherein said C₁₋₂₀ alkyl, C₃₋₂₀cycloalkyl, C₃₋₂₀ heterocyclyl, aryl and heteroaryl are each substitutedby one or more groups selected from:

 -L²—OH, -L²—NH₂, -L²—SH and -L²-M, and wherein said C₁₋₂₀ alkyl isuninterrupted or interrupted by N(R″), O, S or arylene, wherein R″ is asdefined in claim 1; X¹ is a single bond, C(R″)(R′″), N(R″) or O, whereinR″ is as defined in claim 1 and R′″ is H, C₁₋₆ alkyl or aryl; Prot is aprotecting group which is a precursor to a —CH═CH₂ group, wherein Protis selected from 7-oxabicyclo[2.2.1]hept-2-yl, an organometallic group,and a 1,2-dioxygenated substrate; L² is a single bond, C₁₋₆ alkylene,arylene, -arylene-C₁₋₆ alkylene- or -C₁₋₆ alkylene -arylene-, whereineach of said C₁₋₆ alkylene groups is uninterrupted or interrupted byN(R″), O, S or arylene, wherein R″ is as defined in claim 1, providedthat when L² is a single bond the groups

-L²-OH, -L²-NH₂ and -L²—SH may not be bonded directly to X; R¹, R² andR³, which may be the same or different, are each selected from H, C₁₋₆alkyl, aryl, cyano, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, halo, carboxy, ester,C₁₋₆ alkoxy, aryloxy, C₁₋₁₀ alkylthio and arylthio; and M is selectedfrom a group that is capable of adhering to a metal, a metal alloy, or ametal salt, and a group which is a precursor of a group that is capableof adhering to a metal, metal alloy or a metal salt, wherein M is agroup which comprises one or more of any one of the following groups: aphosphonic acid group or a salt thereof, a sulfonic acid group or a saltthereof, a carboxylic acid group or a salt thereof, a sulfonamide group,and C(O)NH₂, or wherein M is -P(═O)(OR⁴)₂ or

wherein R⁴ is C₁₋₆ alkyl or aryl; and Y is H, C₁₋₆ alkyl, aryl, —OH, —SHor NH₂.
 3. A compound according to claim 2 wherein M is selected from:(a) P(═O)(OR⁴)₂;

(c) —C(═O)OH; (d) —CY(COOH)₂; (e) —S (═O)₂OH; (f) —CY[S(═O)₂OH]₂; (g)—C(═O)NH₂; (h) —CY[C(═O)NH₂]₂; (i) —S(═O)₂NH₂; and (j) —CY[S(═O)₂NH₂]₂,wherein R⁴ is C₁₋₆ alkyl or aryl; and Y is H, C₁₋₆ alkyl, aryl, —OH, —SHor NH₂.
 4. A compound according to claim 1, which compound is selectedfrom: [4-(Diazo(phenyl)methyl)phenyl]methanol,7-Oxa-bicyclo[2.2.1]hept-5-ene-2-carboxylicacid-4-(diazo-phenylmethyl)-benzyl ester,1-(allyloxymethyl)-4-(diazo(phenyl)methyl)benzene and[4-(Diazo-phenyl-methyl)-benzyl] phosphonic acid diethyl ester.
 5. Acompound according to claim 1 wherein said group which comprises aplurality of —OH, —NH₂ or —SH moieties is a polyol, a polythiol, a groupcontaining a plurality of amino groups, or a group of the followingstructure:

in which each R⁴ , which may be the same or different, is OH, NH₂ or SH.6. A compound according to claim 1 wherein R is aryl or heteroaryl,which aryl or heteroaryl is unsubstituted or substituted by one or twogroups, which groups are independently selected from C₁₋₆ alkyl, aryl,cyano, amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonicacid, sulfonyl and -L_(B)-W_(B), wherein L_(B) and W_(B) are as definedin claim
 1. 7. A compound according to claim 1 wherein: L_(A) is C₁₋₂₀alkylene which is substituted or unsubstituted and uninterrupted orinterrupted by N(R″), O, S or arylene, wherein R″ is H, C₁₋₆ alkyl oraryl; and R is aryl or heteroaryl, which aryl or heteroaryl isunsubstituted or substituted by one or two groups, which groups areindependently selected from C₁₋₆ alkyl, aryl, cyano, amino, keto, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, hydroxy, halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, haloalkyl,thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl and-L_(B)-W_(B), wherein L_(B) is as defined above for L_(A) and is thesame as or different from L_(A), and wherein W_(B) is as defined inclaim
 1. 8. A compound according to claim 1 wherein: L_(A) is C₁₋₂₀alkylene which is substituted or unsubstituted and uninterrupted orinterrupted by N(R″), O, S or arylene, wherein R″ is H, C₁₋₆ alkyl oraryl; y is 1; and R is aryl or heteroaryl, which aryl or heteroaryl isunsubstituted or substituted by one group, which group is selected fromC₁₋₆ alkyl, aryl, cyano, amino, keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido, hydroxy,halo, carboxy, ester, C₁₋₁₀) 6alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀alkylthio, arylthio, sulfonic acid, sulfonyl and -L_(B)-W_(B), whereinL_(B) is as defined above for L_(A) and is the same as or different fromL_(A), and wherein W_(B) is as defined in claim
 1. 9. A compoundaccording to claim 1 wherein: L_(A) is C₁₋₂₀ alkylene which issubstituted or unsubstituted and uninterrupted or interrupted by N(R″),O, S or arylene, wherein R″ is H, C₁₋₆ alkyl or aryl; A is an aryl ring;y is 1; and R is aryl, which aryl is unsubstituted or substituted by onegroup, which group is selected from C₁₋₆ alkyl, aryl, cyano, amino,keto, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino,arylalkylamino, amido, hydroxy, halo, carboxy, ester, C₁₋₆ alkoxy,aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid,sulfonyl and -L_(B)-W_(B), wherein L_(B) is as defined above for L_(A)and is the same as or different from L_(A), and wherein W_(B) is asdefined in claim
 1. 10. A compound according to claim 1 wherein: L_(A)is C₁₋₂₀ alkylene which is substituted or unsubstituted anduninterrupted or interrupted by N(R″), O, S or arylene, wherein R″ is H,C₁₋₆ alkyl or aryl; and R is aryl or heteroaryl, which aryl orheteroaryl is unsubstituted.
 11. A compound according to claim 1wherein: L_(A) is C₁₋₂₀ alkylene which is substituted or unsubstitutedand uninterrupted or interrupted by N(R″), O, S or arylene, wherein R″is H, C₁₋₆ alkyl or aryl; A is an aryl ring; y is 1; and R is aryl,which aryl is unsubstituted.
 12. A compound according to claim 1wherein: L_(A) is C₁₋₂₀ alkylene which is substituted or unsubstitutedand uninterrupted or interrupted by N(R″), O, S or arylene, wherein R″is H, C₁₋₆ alkyl or aryl; A is phenyl; y is 1; and R is phenyl, whichphenyl is unsubstituted or substituted by one group, which group isselected from C₁₋₆ alkyl, aryl, cyano, amino, keto, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,hydroxy, halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, haloalkyl, thiol,C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl and -L_(B)-W_(B),wherein L_(B) is as defined above for L_(A) and is the same as ordifferent from L_(A), and wherein W_(B) is as defined in claim
 1. 13. Acompound according to claim 1 wherein: L_(A) is C₁₋₆ alkylene which isuninterrupted or interrupted by O; A is phenyl; y is 1; and R is phenyl,which phenyl is unsubstituted or substituted by one group, which groupis selected from C₁₋₆ alkyl, aryl, cyano, amino, keto, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,hydroxy, halo, carboxy, ester, C₁₋₆ alkoxy, aryloxy, haloalkyl, thiol,C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl and -L_(B)-W_(B),wherein L_(B) is as defined above for L_(A) and is the same as ordifferent from L_(A), and wherein W_(B) is as defined in claim
 1. 14. Acompound according to claim 1 wherein: L_(A) is C₁₋₆ alkylene which isuninterrupted or interrupted by O; A is phenyl; y is 1; and R isunsubstituted phenyl.
 15. A process for producing a substrate having afunctionalised surface, which process comprises: (a) contacting thesubstrate with a carbene precursor, which carbene precursor is acompound as defined in claim 1; and (b) generating a carbene reactiveintermediate from the carbene precursor so that it reacts with thesubstrate to functionalise the surface, thereby yielding said substratehaving a functionalised surface.
 16. A process according to claim 15wherein the carbene precursor is a compound selected from:[4-(Diazo(phenyl)methyl)phenyl]methanol,7-Oxa-bicyclo[2.2.1]hept-5-ene-2-carboxylicacid-4-(diazo-phenylmethyl)-benzyl ester,1-(allyloxymethyl)-4-(diazo(phenyl)methyl)benzene and[4-(Diazo-phenyl-methyl)-benzyl] phosphonic acid diethyl ester.
 17. Aprocess according to claim 15 wherein the substrate comprises a polymer,an inorganic material, a pigment, a nanoparticle, a microparticle,textile, paper, a thermoplastic resin or a thermosetting resin.
 18. Aprocess according to claim 17 wherein the polymer is selected frompolyolefins, polyesters, epoxy resins, polyacrylates, polyacrylics,polyamides, polyimides, polystyrenics, polytetrafluoroethylene,polyglycosides, polypeptides, polycarbonates, polyethers, polyketones,rubbers, polysulfones, polyurethanes, polyvinyls, cellulose and blockcopolymers, and wherein the nanoparticle is C₆₀ or a nanotube, andwherein the inorganic material is selected from silica, alumina,titania, glass, an allotrope of carbon, a metal salt, a metal other thanan alkali metal or an alkaline earth metal, and an alloy of a metalother than an alkali metal or an alkaline earth metal.
 19. A processaccording to claim 15 which further comprises: contacting thefunctionalised surface of said substrate, or a part thereof, with anadherend, under conditions which cause adhesion of said substrate tosaid adherend.
 20. A process according to claim 19 wherein wherein theadherend comprises a polymer, an inorganic material, a pigment, ananoparticle, a microparticle, a textile, paper, a thermoplastic resin,a thermosetting resin, a biological cell or biological tissue.
 21. Aprocess according to claim 20 wherein the polymer is selected frompolyolefins, polyesters, epoxy resins, polyacrylates, polyacrylics,polyamides, polyimides, polystyrenics, polytetrafluoroethylene,polyglycosides, polypeptides, polycarbonates, polyethers, polyketones,rubbers, polysulfones, polyurethanes, polyvinyls, cellulose and blockcopolymers, and wherein the nanoparticle is C₆₀ or a nanotube, andwherein the inorganic material is selected from silica, alumina,titania, glass, an allotrope of carbon, a metal salt, a metal other thanan alkali metal or an alkaline earth metal, or an alloy of a metal otherthan an alkali metal or an alkaline earth metal.